CN111318179A - MnO with superstrong oil stain resistance2/carbon fiber cloth composite filtering membrane and preparation method thereof - Google Patents

MnO with superstrong oil stain resistance2/carbon fiber cloth composite filtering membrane and preparation method thereof Download PDF

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Publication number
CN111318179A
CN111318179A CN202010158254.1A CN202010158254A CN111318179A CN 111318179 A CN111318179 A CN 111318179A CN 202010158254 A CN202010158254 A CN 202010158254A CN 111318179 A CN111318179 A CN 111318179A
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carbon fiber
mno
fiber cloth
filtering membrane
composite filtering
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李振宇
雷震
陈靖禹
武元鹏
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Southwest Petroleum University
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Southwest Petroleum University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • 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
    • 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
    • B01D17/08—Thickening liquid suspensions by filtration
    • B01D17/085—Thickening liquid suspensions by filtration with membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention provides MnO with superstrong oil stain resistance2/carbon fiber cloth composite filtration membrane, MnO2The carbon fiber cloth composite filtering membrane comprises a substrate, wherein a micro-nano layer is coated on the outer surface of the substrate and is composed of nano MnO2Micron-sized MnO formed by nanowire2A ball. MnO prepared by the invention2The carbon fiber cloth composite filtering membrane grows a micro-nano layer through hydrothermal reaction, and the micro-nano layer is completely coated on the surface of the carbon fiber layer, so that the whole composite filtering membrane has super-wettability, namely in the airThe super-amphiphilic, underwater super-oleophobic and oil super-hydrophilic performances and the like, and the structure ensures that MnO is2The carbon fiber cloth composite filtering membrane has very high separation efficiency, self-cleaning capacity and high reuse rate.

Description

MnO with superstrong oil stain resistance2/carbon fiber cloth composite filtering membrane and preparation method thereof
Technical Field
The invention relates to the technical field of oil-water separation, in particular to MnO with ultra-strong oil stain resistance2A carbon fiber cloth composite filter membrane, a preparation method and application.
Background
Ocean oil leakage and oil spill frequently occur in the process of oil exploitation and transportation, and a large amount of oil leaks into the water environment of the nature every year, so that not only is the resource waste caused, but also serious environmental pollution is caused, a large amount of animals and plants are poisoned, and the health of human beings is harmed.
There are many existing processing methods, including the following probably: flocculation, membrane filtration, absorption, flotation etc. among these techniques, the membrane filtration technique has easy operation, and the energy consumption is low, advantage such as efficient is the processing mode first choice, but most membrane filtration extremely receives the pollution of oil droplet in the use, has greatly reduced separation efficiency and rate of reuse, therefore it is very necessary to design a filtration membrane that has superstrong anti greasy dirt.
Disclosure of Invention
The invention aims to provide MnO with ultra-strong oil stain resistance2The composite filtering membrane made of carbon fiber cloth is used for realizing the technical effect of improving the oil stain resistance of the filtering membrane.
The invention is realized by the following technical scheme: the MnO2The carbon fiber cloth composite filtering membrane comprises a substrate, wherein a micro-nano layer is coated on the outer surface of the substrate and is composed of nano MnO2Micron-sized MnO formed by nanowire2A ball.
In order to better implement the invention, further, the substrate is selected from carbon fiber cloth.
Another object of the invention is: provides MnO with super-strong oil stain resistance2The preparation method of the carbon fiber cloth composite filtering membrane comprises the following steps:
the preparation method comprises the following preparation steps:
S1：KMnO4preparing an aqueous solution;
mixing KMnO4Ultrasonic dispersing with deionized water, and ultrasonic stirring to obtain KMnO4Dissolving in waterLiquid;
S2：MnO2preparing a carbon fiber cloth composite filtering membrane;
placing carbon fiber cloth on KMnO4Putting the aqueous solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction under the condition of neutral pH, and obtaining MnO after the reaction is finished2A carbon fiber cloth composite filtering membrane.
To better implement the present invention, further, in S2: MnO2Preparing a carbon fiber cloth composite filtering membrane;
placing carbon fiber cloth on KMnO4Putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction under the condition of neutral pH, wherein the reaction conditions are 140-170 ℃ and 2-5 h, and obtaining MnO after the reaction is finished2A carbon fiber cloth composite filtering membrane.
To better implement the present invention, further, in S2: MnO2Preparing a carbon fiber cloth composite filtering membrane;
placing carbon fiber cloth on KMnO4Putting the aqueous solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction under the condition of neutral pH, wherein the reaction conditions are 160 ℃ and 4 hours, and obtaining MnO after the reaction is finished2A carbon fiber cloth composite filtering membrane.
In order to better implement the present invention, further, MnO prepared in step S2 is added2The carbon fiber cloth composite filtering membrane is respectively cleaned by ethanol and water and then dried in a drying oven at the temperature of 60 ℃.
In order to better implement the invention, the pretreatment of the carbon fiber cloth comprises the following steps: and (3) placing the carbon fiber cloth in ethanol for ultrasonic cleaning, and placing the carbon fiber cloth in an oven for drying after cleaning.
The invention also provides another object as MnO2The application of the carbon fiber cloth composite filtering membrane in oil-water separation.
In order to better implement the present invention, further, the MnO2The separation application of the/carbon fiber cloth composite filter membrane in the oil-in-water emulsion.
The reaction mechanism is as follows:
the MnO with super-strong oil stain resistance provided by the invention2The reaction of the carbon fiber cloth composite filtering membrane is as follows:
4MnC4 -+3C+H2O→4MnO2+CO3 2-+2HCO3 -
potassium permanganate is used as a manganese source and reacts with carbon in carbon fibers to obtain hydrophilic manganese dioxide, the hydrophilicity of the manganese dioxide and nano wires of the manganese dioxide are matched with each other to form an aggregate along with the reaction, and the aggregate and the carbon reacted product are accumulated on the surfaces of the fibers due to the fact that more oxygen-containing functional groups exist on the surfaces of the carbon fibers, namely MnO2Nucleation and growth on the surface of the carbon fiber, MnO along with the reaction2The nanostructure is gradually formed, i.e. by MnO2Completely coated to form a final micro-nano structure which is porous and has the characteristics of super-amphiphilicity in the air, super-oleophobicity under water and super-hydrophilicity under oil, thereby enabling MnO of the structure2The/carbon fiber cloth composite filter membrane has super-wettability, and the special super-wettability ensures that MnO is added in the using process2The carbon fiber cloth composite filtering membrane can adsorb water on the surface of the carbon fiber cloth composite filtering membrane to form a water cushion, and dirt of oil can be effectively inhibited through strong repulsion between polar molecules and non-polar molecules, so that MnO is improved2The carbon fiber cloth composite filtering membrane has the anti-fouling performance.
When MnO is prepared2After the/carbon fiber cloth composite filter membrane is greasy, due to MnO thereof2MnO with a large number of oxygen-containing functional groups on the surface of the carbon fiber cloth composite filter membrane for reducing greasy dirt on the surface2The/carbon fiber cloth composite filtering membrane is placed in water and shaken, so that water permeates into polluted MnO2In a carbon fiber cloth composite filter membrane, so that oil is removed from MnO2Extruding in carbon fiber cloth composite filtering membrane to separate MnO2The carbon fiber cloth is compounded with the filtering membrane, so that the aim of further self-cleaning is fulfilled.
The invention provides a method for preparing MnO2The method for compounding the filter membrane with the carbon fiber cloth is simple and easy to operate, and specifically comprises the step of firstly compounding the carbon fiber cloth with the filter membraneThe fiber cloth is ultrasonically cleaned through ethanol, and the ultrasonic cleaning can remove impurities such as slurry on the surface of the carbon fiber cloth, increase oxygen-containing groups and enhance the hydrophilicity.
Mixing KMnO4Performing ultrasonic dispersion with deionized water to obtain KMnO4An aqueous solution, the aqueous solution having a purple color, KMnO4The aqueous solution and the treated carbon fiber cloth are subjected to hydrothermal growth reaction, and MnO with hydrophilicity is formed in the reaction process2Passing MnO continuously during the reaction2The nano wire gradually coats the carbon fiber, the outer surface of the carbon fiber forms a rough structure, and the physical and chemical double modification of the filtering membrane is realized through the reaction, so that the prepared MnO is2The/carbon fiber cloth composite filter membrane has special super-wettability of super-amphiphilicity in air, super-oleophobic property under water and super-hydrophilic property under oil.
In the preparation process, the reaction conditions have important influence on the reaction result, and the carbon fiber cloth is treated under the neutral condition through long-term continuous development, so that the difficulty of subsequent cleaning can be reduced, and the materials and the cost can be saved compared with the conventional acid treatment or alkali treatment.
In the hydrothermal reaction process, the reaction conditions are preferably 140-170 ℃ for 2-5 h, and further preferably 160 ℃ for 4h, so that the growth of the nanowires can be accelerated under the reaction conditions, and the carbon fiber layer is agglomerated and nucleated and coated with the carbon fibers more efficiently.
MnO to be prepared2The carbon fiber cloth composite filtering membrane can be obtained from an oil-water separation experiment through an oil-water separation experiment, the oil-water separation efficiency is high, and particularly the separation efficiency of an oil-water mixture under the driving of gravity>99.8% except for, MnO prepared2Further separation efficiency of carbon fiber cloth composite filter membrane in oil-in-water emulsion>Not only 98%, but also in the separation process, when MnO is present2When the/carbon fiber cloth composite filter membrane is polluted by oil stains, clean MnO can be obtained by simply immersing the/carbon fiber cloth composite filter membrane into water for shaking and cleaning2The carbon fiber cloth composite filtering membrane has strong self-cleaning capability, repeated filtering is carried out after cleaning, and the separation efficiency is not influencedThe repeated utilization rate is high under any influence, and long-term experiments show that the separation efficiency is very good after the separation is repeatedly utilized for 40 times.
The invention has the beneficial effects that:
MnO prepared by the invention2The carbon fiber cloth composite filtering membrane grows a micro-nano layer through hydrothermal reaction, the micro-nano layer is completely coated on the surface of the carbon fiber layer, so that the whole composite filtering membrane has super-wettability, namely super-amphiphilicity in air, super-oleophobic property under water, super-hydrophilic property under oil and the like, and MnO is enabled to be formed by the structure2The carbon fiber cloth composite filtering membrane has very high separation efficiency and anti-fouling capability, and also has self-cleaning capability and higher reuse rate.
MnO prepared by the invention2The preparation method of the/carbon fiber cloth composite filtering membrane is simple, and MnO is efficiently prepared by effectively controlling reaction conditions2The carbon fiber cloth composite filtering membrane does not need to use more chemicals in the preparation process, is more environment-friendly and safer, saves materials, reduces enterprise expenses and improves enterprise income.
MnO prepared by the invention2The carbon fiber cloth composite filtering membrane not only has higher separation efficiency in oil-water separation, but also has very high separation efficiency in a specific oil-in-water emulsion, and long-term experimental verification proves that the separation efficiency in the oil-in-water emulsion is as high as 98%.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings that are required to be used in the present invention will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and it will be apparent to those skilled in the art that other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 shows MnO with ultra-strong oil stain resistance provided by the invention2A schematic diagram for preparing a carbon fiber cloth composite filtering membrane;
FIG. 2 shows MnO with ultra-strong oil stain resistance provided by the invention2The appearance and the component representation of the carbon fiber cloth composite filtering membrane are shown schematically;
FIG. 3 shows MnO with ultra-strong oil stain resistance provided by the invention2A wettability test chart of the carbon fiber cloth composite filter membrane;
FIG. 4 shows MnO with ultra-strong oil stain resistance provided by the invention2A carbon fiber cloth composite filtering membrane anti-fouling performance test chart;
FIG. 5 shows MnO with ultra-strong oil stain resistance provided by the invention2A cleaning performance test chart of the carbon fiber cloth composite filtering membrane;
FIG. 6 shows MnO with ultra-strong oil stain resistance provided by the invention2A carbon fiber cloth composite filtering membrane separation efficiency and flux test chart;
FIG. 7 shows MnO with ultra-strong oil stain resistance provided by the invention2Emulsion separation test chart of carbon fiber cloth composite filter membrane.
Detailed Description
The technical solution of the present invention will be described below with reference to the embodiments of the present invention.
Example (b):
MnO with superstrong oil stain resistance2Composite filtering membrane of carbon fiber cloth
The preparation method comprises the following steps:
s1: pretreatment of carbon fiber cloth:
putting 60 x 60mm carbon fiber cloth in a beaker filled with 50ml ethanol, ultrasonically cleaning for ten minutes, and drying the carbon fiber cloth in a drying oven at 60 ℃;
S2：KMnO4preparation of the aqueous solution
2.212g of KMnO4Adding into 350ml deionized water, and ultrasonically stirring for 10 min to obtain purple solution, namely KMnO4An aqueous solution;
S3：MnO2preparation of/carbon fiber cloth composite filtering membrane
The carbon fiber cloth obtained in the step S1 and the KMnO obtained in the step S2 are mixed4Putting the aqueous solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction under the condition of neutral pH, wherein the reaction condition is 160 ℃ and 4 hours,after the reaction is finished, MnO is obtained2The/carbon fiber cloth composite filter membrane is washed by ethanol and water for 3 times and dried in a drying oven at 60 ℃ to obtain final MnO2A carbon fiber cloth composite filtering membrane.
Comparative example
The preparation method of the carbon fiber cloth film comprises the following steps:
and (3) putting 60 x 60mm carbon fiber cloth in a beaker filled with 50ml ethanol, ultrasonically cleaning for ten minutes, and drying the obtained carbon fiber cloth in an oven at the temperature of 60 ℃.
Experimental data:
the MnO with super-strong oil stain resistance provided by the invention2The reaction of the carbon fiber cloth composite filtering membrane is as follows:
4MnO4 -+3C+H2O→4MnO2+CO3 2-+2HCO3 -
the preparation process of the invention is schematically shown in figure 1.
(1) In the preparation of MnO2The carbon fiber cloth composite filtering membrane pays attention to the change of the structure in real time, the change state diagram is shown as figure 2, wherein, a and b in figure 2 can see that the carbon fiber has smooth surface, does not contain other substances, and gradually forms MnO along with the progress of hydrothermal reaction2Gradually build up on the carbon fiber surface as shown by c and d in FIG. 2, MnO in the further reaction2Gradually increases and slowly agglomerates, and then completely coats the surface of the carbon fiber to form MnO2The structure can be seen from e in figure 2, the thickness of a micro-nano layer formed on the surface of carbon fibers is about 3 micrometers through measurement, the finally prepared composite filtering membrane has special wettability, namely the composite filtering membrane has properties of super-amphiphilicity in air, super-lipophobicity under water and super-hydrophilicity under oil, the composite filtering membrane can be obtained through f in figure 2, a new diffraction peak appears on the membrane, and MnO can be further judged2The presence of crystal planes.
(2) Testing MnO2Wetting property of carbon fiber cloth composite filtering membrane and pure carbon cloth
The test method comprises the following steps: contact Angle (CAs) measurements surface wettability was evaluated using a contact angle meter (OCA 25data physics, Germany). For each sample, at least 5 measurements were made and the average was obtained.
The test results are shown in FIG. 3, and MnO is obtained from a and b in FIG. 32The/carbon fiber cloth composite filter membrane has super-amphiphilicity in air, super-oleophobic property under water and ultra-low rolling angle (namely UWOSA-3 degrees), and can also show the performance of pure carbon cloth, namely showing hydrophobicity in air.
In addition, by adding MnO2The wettability of the/carbon fiber cloth composite filter membrane is tested under water and oil, the test results are shown as c, d and e in figure 3, and the MnO prepared can be seen from the figure2The/carbon fiber cloth composite filter membrane has super-hydrophilicity and super-lipophobicity under water and lower underwater oil adhesive force.
(3) Testing MnO2Anti-fouling performance of/carbon fiber cloth composite filtering membrane
The test method comprises the following steps: MnO to be dried2The/carbon fiber cloth composite filter membrane is pre-wetted by water, then various oils are sprayed on the surface of the filter membrane, and finally the polluted MnO is treated2Soaking the carbon fiber cloth composite filtering membrane in water, spraying various oils on the surface of the carbon fiber cloth composite filtering membrane, and finally carrying out comparative analysis.
And (3) testing results: the MnO 2/carbon fiber cloth composite filter membrane was immersed in water, and as can be seen from a in FIG. 4, heavy oil (. rho.) was obtainedoil>ρwater) And light oil (p)oil<ρwater) Will bounce off without any remaining oil on the membrane. As can be seen from b in FIG. 4, the membrane also shows strong oil stain resistance to crude oil, heavy oil and light oil in the air due to the pre-wetting by water, and further verifies that MnO2After water is adsorbed on the surface of the carbon fiber cloth composite filtering membrane to form the water cushion, dirt of oil can be effectively inhibited through strong repulsive force between polar molecules and non-polar molecules, so that the carbon fiber cloth composite filtering membrane has oil stain resistance.
(4) Testing MnO2Cleaning test of/carbon fiber cloth composite filter membrane after oil contamination
The test method comprises the following steps: MnO to be polluted2Putting the carbon fiber cloth composite filtering membrane into water for oscillation, and measuring the cleanedRear MnO of2The underwater rolling angle of the carbon fiber cloth composite filtering membrane is formed.
The test structure is shown as a in fig. 5: water treated MnO2The/carbon fiber cloth composite filter membrane is placed in the air, the super-oleophobic property of the composite filter membrane is recovered, the oil drops are directly rebounded, MnO2The carbon fiber cloth composite filter membrane has no residue of oil drops, and further has MnO2The/carbon fiber cloth composite filter membrane is placed in a water phase system, and can keep underwater super-oleophobic property and lower underwater oil adhesive force.
In addition, MnO provided by the present invention is further embodied2The carbon fiber cloth composite filtering membrane has excellent antifouling performance, so a contrast test is set, and MnO is to be tested2Contact angle before and after oil stain of the carbon fiber cloth composite filter membrane.
The results are shown in fig. 5 b, and the oils tested are typically cyclohexane, diesel, dichloroethane, chloroform, as can be seen in the figure, MnO2The contact angle of the/carbon fiber cloth composite filtering membrane is not changed, thereby further proving MnO2The antifouling performance of the carbon fiber cloth composite filtering membrane.
(5) Testing MnO2The separation efficiency and the flux of the oil-water mixture are separated by the carbon fiber cloth composite filter membrane;
the test method comprises the following steps: MnO to be prepared2The/carbon fiber cloth composite filter membrane is pre-wetted by water before separation, and MnO is treated by an oil-water separation device2The separation performance of the carbon fiber cloth composite filtering membrane is tested, the effective diameter of a filter of the oil-water separation device is 15 mm, and pre-wetted MnO is added2The carbon fiber cloth composite filter membrane is fixed between glass tubes, light oil and heavy oil represented by n-hexane and dichloroethane respectively are tested, other types of oil (toluene, diesel oil and chloroform) are also tested, a mixture (10ml:10ml) of oil and Sudan III aqueous solution is poured into the glass tubes, and the separation process is completely driven by gravity.
The test results are shown in FIG. 6, where a in FIG. 6 is for the separation of a light aqueous mixture, water can rapidly pass through MnO due to underwater superoleophobic properties2Composite carbon fiber clothFiltration of membranes to thereby enable MnO2Oil is arranged on the top of the carbon fiber cloth composite filtering membrane.
Wherein b in FIG. 6 is for heavy oil/water mixture separation, the entire separation apparatus is tilted during separation to allow water to contact and pass through MnO2The carbon fiber cloth composite filtering membrane can be seen from the figure, and water can pass through MnO2/carbon fiber cloth composite filtration Membrane, MnO2Oil is arranged on the top of the carbon fiber cloth composite filtering membrane.
In the above separation process, the separation efficiency and flux were measured, and the results are shown as c in FIG. 6, which indicates that the MnO was2The carbon fiber cloth composite filtering membrane has high separation efficiency which reaches over 99.8 percent, and the figure also shows that the carbon fiber cloth composite filtering membrane has high separation flux.
(7) Testing MnO2The separation capability of the carbon fiber cloth composite filter membrane on oil-in-water emulsion;
the test method comprises the following steps: by using a homemade separator, shown as a in FIG. 7, in which a plastic syringe is connected under a plastic straw, MnO was measured by the resulting pressure difference between the top and bottom2The carbon fiber cloth composite filter membrane is tightly wrapped in the plastic suction pipe to reduce the distance between the fibers, and the emulsion separation process is completed under the suction of the syringe and the action of the membrane capillary.
The test results are shown in fig. 7 b, where a large number of oil droplets were present in the opaque oil-in-water emulsion before suction, and a clear aqueous solution was obtained after separation, where no oil droplets were present.
The TOC content and separation efficiency of the water-in-oil emulsion were further tested, wherein the TOC content of n-hexane, cyclohexane, toluene and xylene filtrate was 92.3, 33.6, 43.1 and 28.7 mg.L-1. Thus, the removal rates of the film were 98.3%, 99.5%, 99.4%, and 99.6%, respectively.
In conclusion, in different emulsions, the TOC content of the filtrate is lower, and the separation efficiency of the composite membrane is higher.
The MnO provided by the invention is obtained through the experiment2The carbon fiber cloth composite filtering membrane has porous knotsHas excellent underwater super oleophobic performance, so that MnO of the underwater super oleophobic fiber is ensured2The carbon fiber cloth composite filtering membrane can separate oil-water mixture under the driving of gravity, the separation efficiency is high, the separation effect is good, and in addition, the MnO provided by the invention2The carbon fiber cloth composite filtering membrane can effectively remove oil drops in the emulsion due to the hollow layered structure on the membrane; furthermore, MnO provided by the present invention2The carbon fiber cloth composite filtering membrane has stronger anti-fouling capability.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. MnO with superstrong oil stain resistance2The composite filtering membrane for the carbon fiber cloth is characterized in that: the MnO2The carbon fiber cloth composite filtering membrane comprises a substrate, wherein a micro-nano layer is coated on the outer surface of the substrate and is composed of nano MnO2Micron-sized MnO formed by nanowire2A ball.
2. The MnO of claim 1 having superior oil stain resistance2The composite filtering membrane for the carbon fiber cloth is characterized in that: the substrate is selected from carbon fiber cloth.
3. Preparation of the ultra-strong oil stain-resistant MnO of claim 22The method for compounding the filter membrane with the carbon fiber cloth is characterized by comprising the following preparation steps of:
S1：KMnO4preparing an aqueous solution;
mixing KMnO4Ultrasonic dispersing with deionized water, and ultrasonic stirring to obtain KMnO4An aqueous solution;
S2：MnO2preparing a carbon fiber cloth composite filtering membrane;
laying carbon fiber clothIs arranged at KMnO4Putting the aqueous solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction under the condition of neutral pH, and obtaining MnO after the reaction is finished2A carbon fiber cloth composite filtering membrane.
4. The production method according to claim 3,
in said S2: MnO2Preparing a carbon fiber cloth composite filtering membrane;
placing carbon fiber cloth on KMnO4Putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction under the condition of neutral pH, wherein the reaction conditions are 140-170 ℃ and 2-5 h, and obtaining MnO after the reaction is finished2A carbon fiber cloth composite filtering membrane.
5. The production method according to claim 4,
in said S2: MnO2Preparing a carbon fiber cloth composite filtering membrane;
placing carbon fiber cloth on KMnO4Putting the aqueous solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction under the condition of neutral pH, wherein the reaction conditions are 160 ℃ and 4 hours, and obtaining MnO after the reaction is finished2A carbon fiber cloth composite filtering membrane.
6. The method of claim 3, wherein the MnO prepared in step S2 is2The carbon fiber cloth composite filtering membrane is respectively cleaned by ethanol and water and then dried in a drying oven at the temperature of 60 ℃.
7. The preparation method according to claim 3, wherein the step of pretreating the carbon fiber cloth is: and (3) placing the carbon fiber cloth in ethanol for ultrasonic cleaning, and placing the carbon fiber cloth in an oven for drying after cleaning.
8. MnO prepared by the preparation method of any one of claims 3 to 72Composite carbon fiber clothAnd (5) filtering the membrane.
9. The MnO of claim 82The carbon fiber cloth composite filtering membrane is applied to oil-water separation.
10. The MnO of claim 92The composite filtering membrane for the carbon fiber cloth is characterized in that: the MnO2The separation application of the/carbon fiber cloth composite filter membrane in the oil-in-water emulsion.
CN202010158254.1A 2020-03-09 2020-03-09 MnO with superstrong oil stain resistance2/carbon fiber cloth composite filtering membrane and preparation method thereof Pending CN111318179A (en)

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CN115672270A (en) * 2022-10-21 2023-02-03 爱科美材料科技(南通)有限公司 Preparation method of porous carbon nano manganese dioxide composite material for oil-water separation

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Application publication date: 20200623