CN113491960A - High-temperature-resistant oil-water separation membrane and preparation method and application thereof - Google Patents
High-temperature-resistant oil-water separation membrane and preparation method and application thereof Download PDFInfo
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- CN113491960A CN113491960A CN202010261630.XA CN202010261630A CN113491960A CN 113491960 A CN113491960 A CN 113491960A CN 202010261630 A CN202010261630 A CN 202010261630A CN 113491960 A CN113491960 A CN 113491960A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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Abstract
The invention discloses a high-temperature-resistant oil-water separation membrane and a preparation method and application thereof. The high-temperature-resistant oil-water separation membrane has a super-hydrophobic micro/nano binary coarse structure and a continuous three-dimensional reticular structure, wherein the super-hydrophobic micro/nano binary coarse structure consists of polyimide nano fibers and polyimide micro/nano spheres, and the polyimide nano fibers are tightly wrapped on the surfaces of the polyimide micro/nano spheres and have better mechanical properties and super-hydrophobic stability. The preparation method has the advantages of simple preparation flow, easily controlled process, low production cost and the like, and the prepared high-temperature-resistant oil-water separation membrane has uniform and excellent super-hydrophobicity on the surface of the membrane and has super-hydrophobicity on each layer of micro-nano fiber plane inside the membrane, so that the membrane has high flux and excellent high-temperature-resistant and solvent-resistant properties.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a high-temperature-resistant oil-water separation membrane, and a preparation method and application thereof.
Background
Oily waste water generated by ocean oil leakage, industrial waste oil, domestic oil and the like seriously damages the ecological environment and harms human health, and the oil-water separation is more and more valued by people.
One of the difficulties in oil-water separation is the separation of high viscosity oils, and although membranes with super-wetting properties have received extensive attention and evidence in separating various oil-water mixtures, they are primarily limited to the treatment of light oil-water mixtures. Membrane process separation of thick oil/water remains a significant challenge due to the high density and viscosity of thick oil. Such oils are very prone to adhere and contaminate separation materials and facilities, causing functional failure thereof, and many super-wetting materials are also unfortunate.
Separation of high viscosity oil/water mixtures has heretofore relied primarily on electrically driven processes such as high power centrifuges, high temperature vigorous agitation, and the like. These conventional separation techniques have high energy consumption and high operation cost, and it is difficult to achieve high separation accuracy.
Chinese patent CN 107261856A discloses a polyphenylene sulfide superfine fiber oil-water separation membrane and a preparation method thereof, wherein hydrophobic particles are sprayed on the superfine surface of the super-hydrophobic polyphenylene sulfide, and then the polyphenylene sulfide superfine fiber oil-water separation membrane with a three-dimensional net structure is formed by the heat bonding of polyvinylidene fluoride micro-nano powder adhesive, and the membrane can be widely used in membrane separation processes based on the hydrophobic membrane, such as membrane distillation, pervaporation, membrane extraction and the like; however, the preparation steps are complicated, and the thermal adhesive is not resistant to high temperature, so that inorganic particles and an organic matrix are easily peeled off in the actual separation process.
Chinese patent 201810912002.6 discloses an oil-resistant and high-temperature-resistant filter cloth for oil-water separation, which is constructed by adopting a carbon nanotube stainless steel net, acrylate rubber and Tebutron cloth fiber, and although the filter cloth is oil-resistant and high-temperature-resistant, the filter cloth has high cost, complex preparation method and poor flexibility, and the application of the filter cloth is limited.
Disclosure of Invention
The invention mainly aims to provide a high-temperature-resistant oil-water separation membrane, and a preparation method and application thereof, so that the defects of the prior art are overcome.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a high-temperature-resistant oil-water separation membrane which is provided with a super-hydrophobic micro/nano binary rough structure and a continuous three-dimensional reticular structure, wherein the super-hydrophobic micro/nano binary rough structure is composed of polyimide nano fibers and polyimide micro/nano spheres, and the polyimide nano fibers are tightly arranged on the surfaces of the polyimide micro/nano spheres in a layer-by-layer wrapping or layer-by-layer stacking mode.
Further, the thickness of the high-temperature-resistant oil-water separation membrane is 80-200 mu m, the porosity of the high-temperature-resistant oil-water separation membrane is higher than 95%, the static contact angle between the surface of the high-temperature-resistant oil-water separation membrane and water is 140-155 degrees, the rolling angle is 3-8 degrees, the oil-water separation efficiency of the high-temperature-resistant oil-water separation membrane is more than 99%, and the flux is 4.6 multiplied by 104L·m-2·h-1·bar-1～6.2× 104L·m-2·h-1·bar-1。
The embodiment of the invention also provides a preparation method of the high-temperature-resistant oil-water separation membrane, which comprises the following steps:
respectively providing a polyimide electrostatic spraying solution and a polyimide electrostatic spinning solution;
and simultaneously applying the polyimide electrostatic spraying solution and the polyimide electrostatic spinning solution on a substrate in a mode of combining electrostatic spraying and electrostatic spinning, and then carrying out hot-pressing treatment to obtain the high-temperature-resistant oil-water separation membrane.
Further, the polyimide electrostatic spraying solution comprises the following components in parts by mass: 4-12 parts of polyimide and 88-96 parts of solvent.
Further, the polyimide electrostatic spinning solution comprises the following components in parts by mass: 15-30 parts of polyimide and 70-85 parts of solvent.
Further, the solvent comprises any one or the combination of more than two of N-methyl pyrrolidone, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, 1, 4-dioxane, chloroform and dichloromethane.
The embodiment of the invention also provides the high-temperature-resistant oil-water separation membrane prepared by the method.
The embodiment of the invention also provides application of the high-temperature-resistant oil-water separation membrane in the field of oil-water separation or membrane distillation.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-temperature-resistant oil-water separation membrane is a composite membrane with a super-hydrophobic binary rough and three-dimensional network structure, wherein the polyimide micro-nanospheres are wrapped by the nanofibers, the surface of the membrane has uniform and excellent super-hydrophobicity, and each layer of micro-nanofiber plane in the membrane has super-hydrophobicity, so that the high-temperature-resistant oil-water separation membrane has high flux and the separation efficiency is up to 99%.
(2) The preparation method of the high-temperature-resistant oil-water separation membrane is simple, the process is simple and controllable, and the large-scale production is easy to realize; only by the mode of combining electrostatic spraying and electrostatic spinning, the nano-fiber layer formed by electrostatic spinning wraps the micro-nanospheres formed by spraying, so that a super-hydrophobic binary rough and three-dimensional net-shaped structure of polyimide micro-nanospheres wrapped by nano-fibers can be constructed in one step, and on a receiving roller, the micro-nanofiber and residual solvents of the nanospheres are volatilized together, so that the combination of the fibers and the balls is more stable; the composite membrane prepared by the method can be applied to oil-water separation, membrane distillation and the like, is particularly suitable for high-efficiency separation of high-viscosity oil at high temperature, and effectively solves the problem of high-viscosity oil/water separation.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIGS. 1a and 1b are Surface (SEM) photographs of the high temperature resistant oil-water separation membrane prepared in example 1.
FIGS. 2a and 2b are Surface (SEM) photographs of the high temperature resistant oil-water separation membrane prepared in example 1 after being soaked in a solvent D5 at 80 ℃ for 30 hours.
FIG. 3a is a result of a water contact angle test of the high temperature-resistant oil-water separation membrane prepared in example 1 at 80 ℃.
FIG. 3b shows the D5 contact angle of water under oil of the high temperature resistant oil-water separation membrane prepared in example 1 at 80 ℃.
FIG. 4a is a schematic diagram of the emulsion before separation of D5/water emulsion in the thermostable oil-water separation membrane prepared in example 1 at 80 ℃.
FIG. 4b is a schematic diagram of the filtrate collected after separation of D5/water emulsion from the thermostable oil-water separation membrane prepared in example 1 at 80 ℃.
FIG. 4c is a schematic diagram showing the particle size of the high temperature resistant membrane for oil-water separation D5/water emulsion prepared in example 1 at 80 ℃.
FIG. 4D is a schematic diagram showing the particle size of the high temperature resistant membrane D5/water emulsion prepared in example 1 after separation at 80 ℃.
FIG. 5 is a Surface (SEM) view of an oil-water separation membrane prepared in comparative example 1.
FIG. 6 is a Surface (SEM) view of an oil-water separation membrane prepared in comparative example 2.
Detailed Description
The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
In view of the shortcomings of the prior art, the present inventors have long studied and practiced in great numbers to provide the technical solutions of the present invention, and further explain the technical solutions, the implementation processes and principles thereof as follows.
One aspect of the embodiment of the invention provides a high-temperature-resistant oil-water separation membrane, which has a super-hydrophobic micro/nano binary rough structure and a continuous three-dimensional reticular structure, wherein the super-hydrophobic micro/nano binary rough structure is composed of polyimide nano fibers and polyimide micro/nano spheres, and the polyimide nano fibers are tightly arranged on the surfaces of the polyimide micro/nano spheres in a layer-by-layer wrapping or layer-by-layer stacking mode.
In some preferred embodiments, the polyimide nanofibers have a diameter of 0.1 to 1 μm.
In some preferred embodiments, the diameter of the polyimide micro/nanospheres is 0.5-5 μm.
In some preferred embodiments, the thickness of the high-temperature-resistant oil-water separation membrane is 80-200 μm, the porosity of the high-temperature-resistant oil-water separation membrane is higher than 95%, the static contact angle of the surface of the high-temperature-resistant oil-water separation membrane with water is 140-155 DEG, the rolling angle is 3-8 DEG, the oil-water separation efficiency of the high-temperature-resistant oil-water separation membrane is above 99%, and the flux is 4.6 × 104L·m-2·h-1·bar-1～6.2 ×104L·m-2·h-1·bar-1。
The polyimide material contains the phthalimide ring, so that the rigidity of a molecular chain is enhanced, and the polyimide has good mechanical property, thermal stability and corrosion resistance; the high-viscosity oil is very sensitive to temperature, and the viscosity of the high-viscosity oil is rapidly reduced along with the increase of the temperature, so that the super-hydrophobic structure separation membrane is constructed by the inventor by utilizing the temperature sensitivity of the high-viscosity oil and selecting a high-temperature-resistant polyimide material, and can be used for efficiently separating the high-viscosity oil and the high-temperature oil.
Another aspect of the embodiments of the present invention provides a method for preparing a high temperature resistant oil-water separation membrane, including:
respectively providing a polyimide electrostatic spraying solution and a polyimide electrostatic spinning solution;
and simultaneously applying the polyimide electrostatic spraying solution and the polyimide electrostatic spinning solution on a substrate in a mode of combining electrostatic spraying and electrostatic spinning, and then carrying out hot-pressing treatment to obtain the high-temperature-resistant oil-water separation membrane.
In some preferred embodiments, the preparation method comprises: and dissolving polyimide in a solvent to form the polyimide electrostatic spraying solution.
Further, the polyimide electrostatic spraying solution comprises the following components in parts by mass: 4-12 parts of polyimide and 88-96 parts of solvent.
In some preferred embodiments, the preparation method comprises: dissolving polyimide in a solvent to form the polyimide electrospinning solution.
Further, the polyimide electrostatic spinning solution comprises the following components in parts by mass: 15-30 parts of polyimide and 70-85 parts of solvent.
Further, the solvent may include any one or a combination of two or more of N-methylpyrrolidone, dimethylsulfoxide, dimethylacetamide, dimethylformamide, 1, 4-dioxane, chloroform, dichloromethane, and the like, but is not limited thereto.
In some preferable schemes of the embodiments of the present invention, the preparation method of the high temperature resistant oil-water separation membrane includes:
disposing the substrate on a receiving mechanism;
and respectively and oppositely spraying the polyimide electrostatic spraying solution and the polyimide electrostatic spinning solution to the surface of the substrate from two sides of the receiving mechanism simultaneously in a mode of combining electrostatic spraying and electrostatic spinning.
In some preferred embodiments, the electrostatic spraying employs process conditions including: the diameter of the spray head is 0.2-1.0mm, the advancing speed of the polyimide electrostatic spraying solution is 0.2-5mL/h, the electrostatic spraying applied voltage is 5-20kV, the receiving distance is 10-20cm, the rotating speed of the receiving mechanism is 20-500rpm, the electrostatic spraying environment temperature is 20-60 ℃, the electrostatic spraying environment relative humidity is 20-80%, and the electrostatic spraying time is 0.5-20 h.
In some preferred embodiments, the electrospinning employs process conditions including: the diameter of a spray head is 0.5-1.0mm, the advancing speed of the polyimide electrostatic spinning solution is 0.2-5mL/h, the electrostatic spinning applied voltage is 5-20kV, the receiving distance is 10-20cm, the rotating speed of a receiving mechanism is 20-500rpm, the electrostatic spinning ambient temperature is 20-60 ℃, the electrostatic spinning ambient relative humidity is 20-80%, and the electrostatic spinning time is 0.5-20 h.
In some preferable schemes of the embodiment of the invention, the temperature of the hot pressing treatment is 80-150 ℃ and the time is 6-20 h.
Further, the substrate includes a non-woven fabric.
Further, the nonwoven fabric may include one or both of a polyester nonwoven fabric or a polypropylene nonwoven fabric, but is not limited thereto.
In some preferred embodiments, the receiving mechanism comprises a receiving roller.
In some preferable schemes of the embodiment of the invention, the preparation method of the high-temperature-resistant oil-water separation membrane is carried out according to the following steps:
step (1): dissolving polyimide in a solvent to prepare a polyimide electrostatic spraying solution a and a polyimide electrostatic spinning solution b;
step (2): respectively installing the solutions a and b obtained in the step (1) on the left side and the right side of an equipment receiving roller, and spraying the solutions to non-woven fabrics wrapped on the equipment receiving roller through electrostatic spraying and electrostatic spinning simultaneously;
and (3): and (3) carrying out hot pressing treatment on the polyimide composite membrane obtained by opposite spraying for 6-20h in an oven at the temperature of 80-150 ℃ to obtain the high-temperature-resistant oil-water separation membrane.
In some more specific preferred embodiments of the present invention, a method for preparing a high temperature resistant oil-water separation membrane includes the following steps:
step (1): dissolving polyimide in a solvent to prepare a polyimide electrostatic spraying solution a and a polyimide electrostatic spinning solution b;
step (2): respectively installing the solutions a and b obtained in the step (1) on the left side and the right side of an equipment receiving roller, and spraying the solutions to non-woven fabrics wrapped on the equipment receiving roller through electrostatic spraying and electrostatic spinning simultaneously; wherein the electrostatic spraying parameters are as follows: the diameter of a spray head is 0.2-1.0mm, the liquid propelling speed is 0.2-5mL/h, the spraying applied voltage is 5-20kV, the receiving distance is 10-20cm, the rotating speed of a receiving roller is 20-500rpm, the electrostatic spraying environment temperature is 20-60 ℃, the relative humidity of the spraying environment is 20-80%, and the spraying time is 0.5-20 h; the electrostatic spinning parameters are as follows: the diameter of a spray head is 0.5-1.0mm, the liquid propelling speed is 0.2-5mL/h, the spraying applied voltage is 5-20kV, the receiving distance is 10-20cm, the rotating speed of a receiving roller is 20-500rpm, the temperature of the electrostatic spinning environment is 20-60 ℃, the relative humidity of the spinning environment is 20-80%, and the spraying time is 0.5-20 h;
and (3): and (3) carrying out hot pressing treatment on the polyimide composite membrane obtained by opposite spraying for 6-20h in an oven at the temperature of 80-150 ℃ to obtain the high-temperature-resistant oil-water separation membrane.
According to the preparation method of the high-temperature-resistant oil-water separation membrane, the nano-fiber layer formed by electrostatic spinning wraps the micro-nanospheres formed by spraying layer by layer in a mode of combining electrostatic spraying and electrostatic spinning, so that a super-hydrophobic binary rough and three-dimensional net-shaped structure of the polyimide micro-nanospheres wrapped by the nano-fiber can be constructed in one step, and the micro-nanofiber and residual solvent of the nanospheres are volatilized together on a receiving roller, so that the fiber and the nanospheres are combined more stably.
One aspect of the embodiment of the invention also provides the high-temperature-resistant oil-water separation membrane prepared by the method. In another aspect of the embodiments of the present invention, an application of the foregoing high temperature resistant oil-water separation membrane in oil-water separation or membrane distillation is provided.
In some preferable aspects of the embodiments of the present invention, the aforementioned high temperature resistant oil-water separation membrane is particularly suitable for high viscosity oil/water separation at high temperature.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
(1) A20X 30cm polyester nonwoven fabric was fixed to a receiving roll of an electrostatic spraying apparatus.
(2) Polyimide is dissolved in N-methyl pyrrolidone solvent to prepare a polyimide solution a with the mass concentration of 12% and a polyimide solution b with the mass concentration of 30%.
(3) And (3) loading the solution a into an injector, and installing the injector on the left side of a receiving roller of the equipment to perform electrostatic spraying, wherein the electrostatic spraying parameters are as follows: the diameter of a spray head is 0.7mm, the liquid propelling speed is 1mL/h, the spraying applied voltage is 10kV, the receiving distance is 15cm, the rotating speed of a receiving roller is 200rpm, the electrostatic spraying environment temperature is 40 ℃, the relative humidity of the spraying environment is 50%, and the spraying time is 8 h; and (3) loading the solution b into an injector, and installing the injector on the right side of a receiving roller of the device to perform electrostatic spinning, wherein the electrostatic spinning parameters are as follows: the diameter of a spray head is 0.9mm, the liquid propelling speed is 1mL/h, the spraying applied voltage is 10kV, the receiving distance is 15cm, the rotating speed of a receiving roller is 200rpm, the electrostatic spinning environment temperature is 40 ℃, the spinning environment relative humidity is 50%, and the spraying time is 8 h; both sides are opened simultaneously and finished simultaneously.
(4) And taking the sprayed film down from the receiving roller, and putting the film in a 100 ℃ oven for hot pressing for 12 hours to obtain the high-temperature-resistant oil-water separation film.
The thickness of the oil-water separation membrane of the product obtained in the embodiment is 120 μm.
As shown in FIGS. 1a and 1b, the surface of the film of this example is a continuous three-dimensional network structure.
As shown in FIGS. 3a and 3b, under the high temperature condition of 80 ℃, the contact angles of water and oil of the film under water are respectively as high as 150 degrees and 168 degrees, and the rolling angle is 5 degrees.
As can be seen from FIGS. 2a and 2b, the surface morphology of the film is not substantially changed after the film is soaked in decamethylcyclopentasiloxane (D5) oil solvent for 30 hours at 80 ℃, which indicates that the film has better high temperature resistance and solvent resistance.
The high-temperature-resistant oil-water separation membrane prepared in example 1 was subjected to an oil-water emulsion separation test by a gravity filtration device, and a micron-sized D5 emulsion was separated with water at a mass ratio of 99: 1, and the membraneIs favorable for demulsification and can achieve the purpose of oil-water separation. The effective separation efficiency for DS/water emulsion at 80 ℃ is 99.2%, and the flux is 4.6X 104L·m-2.h-1·bar-1. The emulsion before separation is stable and milk white as shown in fig. 4a and 4c, and the filtrate has high purity, clarity and transparency as shown in fig. 4b and 4 d.
Example 2
(1) A20X 30cm polyester nonwoven fabric was fixed to a receiving roll of an electrostatic spraying apparatus.
(2) Polyimide is dissolved in dimethyl sulfoxide solvent to prepare a polyimide solution a with the mass concentration of 4% and a polyimide solution b with the mass concentration of 15%.
(3) And (3) loading the solution a into an injector, and installing the injector on the left side of a receiving roller of the equipment to perform electrostatic spraying, wherein the electrostatic spraying parameters are as follows: the diameter of a spray head is 0.2mm, the liquid propelling speed is 0.2mL/h, the spraying applied voltage is 5kV, the receiving distance is 10cm, the rotating speed of a receiving roller is 100rpm, the electrostatic spraying environment temperature is 20 ℃, the relative humidity of the spraying environment is 20%, and the spraying time is 8 h; and (3) loading the solution b into an injector, and installing the injector on the right side of a receiving roller of the device to perform electrostatic spinning, wherein the electrostatic spinning parameters are as follows: the diameter of a spray head is 0.5mm, the liquid propelling speed is 0.2mL/h, the spraying applied voltage is 5kV, the receiving distance is 10cm, the rotating speed of a receiving roller is 100rpm, the electrostatic spinning environment temperature is 20 ℃, the spinning environment relative humidity is 20%, and the spraying time is 8 h; both sides are opened simultaneously and finished simultaneously.
(4) And taking the sprayed film down from the receiving roller, and putting the film in a 120 ℃ oven for hot pressing for 10 hours to obtain the high-temperature-resistant oil-water separation film.
The thickness of the oil-water separation membrane of the product obtained in the embodiment is 130 μm. Under the high temperature condition of 80 ℃, the water contact angles of water and oil of the film are respectively as high as 148 degrees and 165 degrees, and the rolling angle is 6 degrees. At the temperature of 80 ℃, the surface appearance of the film is basically not changed after the film is soaked in a soybean oil solvent for 30 hours, which shows that the film has better high temperature resistance and solvent resistance.
The membrane is used for oil-water emulsion separation test to separate micron-sized soybean oil emulsion, the mass ratio of soybean oil to water is 99: 1, and the membrane is favorable for demulsification and can achieve the purpose of oil-water separation. Effective component for soybean oil/water emulsion at 25 deg.CThe separation efficiency is 90%, and the flux is 200 L.m-2·h-1·bar-1(ii) a The effective separation efficiency of the soybean oil/water emulsion at 80 ℃ is 95 percent, and the flux is 600 multiplied by 104L·m-2·h-1·bar-1。
Example 3
(1) A20X 30cm polypropylene nonwoven was fixed to a receiving roll of an electrostatic spraying device.
(2) Polyimide is dissolved in a dimethylacetamide solvent to prepare a polyimide solution a with the mass concentration of 12% and a polyimide solution b with the mass concentration of 30%.
(3) And (3) loading the solution a into an injector, and installing the injector on the left side of a receiving roller of the equipment to perform electrostatic spraying, wherein the electrostatic spraying parameters are as follows: the diameter of a spray head is 0.8mm, the liquid propelling speed is 5mL/h, the spraying applied voltage is 20kV, the receiving distance is 20cm, the rotating speed of a receiving roller is 500rpm, the electrostatic spraying environment temperature is 30 ℃, the relative humidity of the spraying environment is 30%, and the spraying time is 20 h; and (3) loading the solution b into an injector, and installing the injector on the right side of a receiving roller of the device to perform electrostatic spinning, wherein the electrostatic spinning parameters are as follows: the diameter of a spray head is 0.7mm, the liquid propelling speed is 5mL/h, the spraying applied voltage is 20kV, the receiving distance is 20cm, the rotating speed of a receiving roller is 500rpm, the electrostatic spinning environment temperature is 30 ℃, the spinning environment relative humidity is 30%, and the spraying time is 20 h; both sides are opened simultaneously and finished simultaneously.
(4) And taking the sprayed film down from the receiving roller, and placing the film in a 90 ℃ oven for hot pressing for 15h to obtain the high-temperature-resistant oil-water separation film.
The thickness of the oil-water separation membrane of the product obtained in the embodiment is 130 μm. Under the high temperature condition of 80 ℃, the water contact angles of the film under water and oil are respectively as high as 148 degrees and 170 degrees, and the rolling angle is 4 degrees. The membrane is used for oil-water emulsion separation test, micron-sized heavy oil (API value is 17 degrees) emulsion is separated, and the mass ratio of the heavy oil to water is 99.5: 0.5, the membrane is beneficial to demulsification and can achieve the purpose of oil-water separation. The effective separation efficiency of the heavy oil/water emulsion at 25 ℃ is 85 percent, and the flux is 210 L.m-2·h-1·bar-1(ii) a The effective separation efficiency of the heavy oil/water emulsion at 80 ℃ is 99 percent, and the flux is 620 multiplied by 104L·m-2·h-1·bar-1。
Example 4
(1) A20X 30cm polyester nonwoven fabric was fixed to a receiving roll of an electrostatic spraying apparatus.
(2) Polyimide is dissolved in a 1, 4-dioxane solvent to prepare a polyimide solution a with the mass concentration of 10% and a polyimide solution b with the mass concentration of 18%.
(3) And (3) loading the solution a into an injector, and installing the injector on the left side of a receiving roller of the equipment to perform electrostatic spraying, wherein the electrostatic spraying parameters are as follows: the diameter of a spray head is 0.9mm, the liquid propelling speed is 1mL/h, the spraying applied voltage is 10kV, the receiving distance is 12cm, the rotating speed of a receiving roller is 300rpm, the electrostatic spraying environment temperature is 30 ℃, the relative humidity of the spraying environment is 30%, and the spraying time is 10 h; and (3) loading the solution b into an injector, and installing the injector on the right side of a receiving roller of the device to perform electrostatic spinning, wherein the electrostatic spinning parameters are as follows: the diameter of a spray head is 0.9mm, the liquid propelling speed is 1mL/h, the spraying applied voltage is 10kV, the receiving distance is 12cm, the rotating speed of a receiving roller is 300rpm, the electrostatic spinning environment temperature is 30 ℃, the spinning environment relative humidity is 30%, and the spraying time is 10 h; both sides are opened simultaneously and finished simultaneously.
(4) And taking the sprayed film down from the receiving roller, and putting the film in a 150 ℃ oven for hot pressing for 6 hours to obtain the high-temperature-resistant oil-water separation film.
The thickness of the oil-water separation membrane of the product obtained in the embodiment is 110 μm. Under the high temperature condition of 80 ℃, the water contact angles of water and oil of the film are respectively as high as 142 degrees and 165 degrees, and the rolling angle is 7 degrees. At the temperature of 80 ℃, the surface appearance of the film is basically not changed after the film is soaked in a soybean oil solvent for 30 hours, which shows that the film has better high temperature resistance and solvent resistance.
The membrane is used for oil-water emulsion separation test, and the micron-sized soybean oil emulsion is separated, the mass ratio of the micron-sized soybean oil emulsion to water is 99: 1, the membrane is favorable for demulsification, and the purpose of oil-water separation can be achieved. The effective separation efficiency of the soybean oil/water emulsion at 80 ℃ is 99 percent, and the flux is 610 L.m-2·h-1·bar-1。
Example 5
(1) A20X 30cm polyester nonwoven fabric was fixed to a receiving roll of an electrostatic spraying apparatus.
(2) Polyimide is dissolved in a chloroform solvent to prepare a polyimide solution a with the mass concentration of 8% and a polyimide solution b with the mass concentration of 20%.
(3) And (3) loading the solution a into an injector, and installing the injector on the left side of a receiving roller of the equipment to perform electrostatic spraying, wherein the electrostatic spraying parameters are as follows: the diameter of a spray head is 1.0mm, the liquid propelling speed is 1mL/h, the spraying applied voltage is 10kV, the receiving distance is 15cm, the rotating speed of a receiving roller is 20rpm, the electrostatic spraying environment temperature is 60 ℃, the relative humidity of the spraying environment is 80%, and the spraying time is 0.5 h; and (3) loading the solution b into an injector, and installing the injector on the right side of a receiving roller of the device to perform electrostatic spinning, wherein the electrostatic spinning parameters are as follows: the diameter of a spray head is 1.0mm, the liquid propelling speed is 1mL/h, the spraying applied voltage is 10kV, the receiving distance is 15cm, the rotating speed of a receiving roller is 200rpm, the electrostatic spinning environment temperature is 60 ℃, the spinning environment relative humidity is 80%, and the spraying time is 0.5 h; both sides are opened simultaneously and finished simultaneously.
(4) And taking the sprayed film down from the receiving roller, and putting the film in an oven at 80 ℃ for hot pressing for 20 hours to obtain the high-temperature-resistant oil-water separation film.
The thickness of the oil-water separation membrane of the product obtained in the embodiment is 80 μm. Under the high temperature condition of 80 ℃, the water contact angles of water and oil of the film are respectively as high as 145 degrees and 165 degrees, and the rolling angle is 6 degrees. At the temperature of 80 ℃, the surface appearance of the film is basically not changed after the film is soaked in a soybean oil solvent for 30 hours, which shows that the film has better high temperature resistance and solvent resistance.
The membrane is used for oil-water emulsion separation test, and the micron-sized soybean oil emulsion is separated, the mass ratio of the micron-sized soybean oil emulsion to water is 99: 1, the membrane is favorable for demulsification, and the purpose of oil-water separation can be achieved. The effective separation efficiency of the soybean oil/water emulsion at 80 ℃ is 99 percent, and the flux is 620 L.m-2·h-1·bar-1。
Comparative example 1
(1) A20X 30cm polyester nonwoven fabric was fixed to a receiving roll of an electrostatic spraying apparatus.
(2) Polyimide is dissolved in N-methyl pyrrolidone solvent to prepare polyimide solution a with the mass concentration of 10%.
(3) Solution a is filled into a syringe and is arranged on the left side of a receiving roller of the equipment for electrostatic spraying, and the electrostatic spraying parameters are as follows: the diameter of the spray head is 0.7mm, the voltage is 10kV, the receiving distance is 15cm, the propelling speed is 1mL/h, the transverse moving (left-right moving) speed of the spraying equipment is 100mm/min, and the spraying time is 25 h.
(4) And taking the sprayed film down from the receiving roller, and putting the film in a 100 ℃ oven for hot pressing for 12 hours to obtain the high-temperature-resistant oil-water separation film.
The thickness of the oil-water separation membrane of the product obtained in the comparative example was 120. mu.m.
As shown in FIG. 5, the surface of the film of this comparative example exhibited a spherical packing morphology.
The oil-water separation membrane prepared in the comparative example 1 was subjected to an oil-water emulsion separation test by a gravity filtration apparatus, and the micron-sized D5 emulsion was separated at a mass ratio of 99: 1 to water, and the membrane had an effective separation efficiency of 45% for D5/water emulsion at 80 ℃ and a flux of 6.0X 104L·m-2·h-1·bar-1. Although the flux is higher, the separation efficiency is low, and after the separation experiment is finished, the particles on the surface of the membrane are seriously fallen off.
Comparative example 2
(1) A20X 30cm polyester nonwoven fabric was fixed to a receiving roll of an electrostatic spraying apparatus.
(2) And dissolving the polyimide in an N-methyl pyrrolidone solvent to prepare a polyimide solution b with the mass concentration of 25%.
(3) And (3) loading the solution b into a syringe, and installing the syringe on the left side of a receiving roller of the equipment for electrostatic spraying, wherein the electrostatic spraying parameters are as follows: the diameter of the spray head is 0.9mm, the voltage is 12kV, the receiving distance is 15cm, the propelling speed is 1mL/h, the transverse moving (left-right moving) speed of the spraying equipment is 100mm/min, and the spraying time is 20 h.
(4) And taking the sprayed film down from the receiving roller, and putting the film in a 100 ℃ oven for hot pressing for 12 hours to obtain the high-temperature-resistant oil-water separation film.
The thickness of the oil-water separation membrane of the product obtained in the comparative example was 120. mu.m.
As shown in FIG. 6, the surface of the film of this comparative example was in the form of nanofibers.
The oil-water separation membrane prepared in the comparative example 2 was subjected to an oil-water emulsion separation test by a gravity filtration device, and the micron-sized D5 emulsion was separated with water at a mass ratio of 99: 1, and the effective separation efficiency of the membrane to 80 ℃ D5/water emulsion was found to be high40% and a flux of 1.0X 104L·m-2·h-1·bar-1The separation efficiency is low.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A high temperature resistant oil-water separation membrane is characterized in that: the high-temperature-resistant oil-water separation membrane is provided with a super-hydrophobic micro/nano binary rough structure and a continuous three-dimensional reticular structure, wherein the super-hydrophobic micro/nano binary rough structure is composed of polyimide nano fibers and polyimide micro/nano spheres, and the polyimide nano fibers are tightly arranged on the surfaces of the polyimide micro/nano spheres in a layer-by-layer wrapping or layer-by-layer stacking mode.
2. The high-temperature-resistant oil-water separation membrane according to claim 1, characterized in that: the diameter of the polyimide nano fiber is 0.1-1 μm, and/or the diameter of the polyimide micro/nano sphere is 0.5-5 μm.
3. The high-temperature-resistant oil-water separation membrane according to claim 1, characterized in that: the thickness of the high-temperature-resistant oil-water separation membrane is 80-200 mu m, the porosity of the high-temperature-resistant oil-water separation membrane is higher than 95%, the static contact angle between the surface of the high-temperature-resistant oil-water separation membrane and water is 140-155 DEG, the rolling angle is 3-8 DEG, the oil-water separation efficiency of the high-temperature-resistant oil-water separation membrane is more than 99%, the flux is 4.6 multiplied by 104L·m-2·h-1·bar-1～6.2×104L·m-2·h-1·bar-1。
4. The method for producing a high-temperature-resistant oil-water separation membrane according to any one of claims 1 to 3, comprising:
respectively providing a polyimide electrostatic spraying solution and a polyimide electrostatic spinning solution;
and simultaneously applying the polyimide electrostatic spraying solution and the polyimide electrostatic spinning solution on a substrate in a mode of combining electrostatic spraying and electrostatic spinning, and then carrying out hot-pressing treatment to obtain the high-temperature-resistant oil-water separation membrane.
5. The method for producing a high-temperature-resistant oil-water separation membrane according to claim 4, comprising: dissolving polyimide in a solvent to form the polyimide electrostatic spraying solution; preferably, the polyimide electrostatic spraying solution comprises the following components in parts by weight: 4-12 parts of polyimide and 88-96 parts of solvent.
And/or, the preparation method comprises the following steps: dissolving polyimide in a solvent to form the polyimide electrospinning solution; preferably, the polyimide electrospinning solution comprises the following components in parts by mass: 15-30 parts of polyimide and 70-85 parts of solvent;
preferably, the solvent includes any one or a combination of two or more of N-methylpyrrolidone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, 1, 4-dioxane, chloroform, and dichloromethane.
6. The method for producing a high-temperature-resistant oil-water separation membrane according to claim 4, comprising:
disposing the substrate on a receiving mechanism;
and respectively and oppositely spraying the polyimide electrostatic spraying solution and the polyimide electrostatic spinning solution to the surface of the substrate from two sides of the receiving mechanism simultaneously in a mode of combining electrostatic spraying and electrostatic spinning.
7. The preparation method of the high-temperature-resistant oil-water separation membrane as claimed in claim 4 or 6, wherein the electrostatic spraying adopts process conditions comprising: the diameter of the spray head is 0.2-1.0mm, the advancing speed of the polyimide electrostatic spraying solution is 0.2-5mL/h, the electrostatic spraying applied voltage is 5-20kV, the receiving distance is 10-20cm, the rotating speed of the receiving mechanism is 20-500rpm, the electrostatic spraying environment temperature is 20-60 ℃, the electrostatic spraying environment relative humidity is 20-80%, and the electrostatic spraying time is 0.5-20 h; and/or the electrostatic spinning adopts the process conditions comprising the following steps: the diameter of a spray head is 0.5-1.0mm, the advancing speed of the polyimide electrostatic spinning solution is 0.2-5mL/h, the electrostatic spinning applied voltage is 5-20kV, the receiving distance is 10-20cm, the rotating speed of a receiving mechanism is 20-500rpm, the electrostatic spinning ambient temperature is 20-60 ℃, the electrostatic spinning ambient relative humidity is 20-80%, and the electrostatic spinning time is 0.5-20 h.
8. The method for producing a high-temperature-resistant oil-water separation membrane according to claim 6, characterized in that: the temperature of the hot pressing treatment is 80-150 ℃, and the time is 6-20 h;
and/or the substrate comprises a non-woven fabric, preferably a polyester non-woven fabric and/or a polypropylene non-woven fabric;
and/or, the receiving mechanism comprises a receiving roller.
9. A high temperature resistant oil-water separation membrane prepared by the method of any one of claims 4 to 8.
10. The use of the high temperature resistant oil-water separation membrane of any one of claims 1-3, 9 in the field of oil-water separation or membrane distillation; preferably, the oil-water separation comprises high viscosity oil/water separation at high temperature.
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