CN-121972014-A - Submerged super-amphiphobic oil-water separation material and preparation method and application thereof

CN121972014ACN 121972014 ACN121972014 ACN 121972014ACN-121972014-A

Abstract

The application belongs to the technical field of oil-water mixture separation materials, and particularly relates to a submerged super-amphiphobic oil-water separation material, and a preparation method and application thereof. The preparation method of the submerged super-amphiphobic oil-water separation material comprises the following steps of (1) conducting photoresist removal, acidification and vacuum plasma pretreatment on carbon fibers, (2) coating and growing Co (OH) 2 nanocrystalline on the surfaces of the pretreated carbon fibers, conducting calcination treatment to convert Co (OH) 2 into Co 3 O 4 , and (3) in-situ converting Co 3 O 4 on the surfaces of the carbon fibers obtained in the step (2) into CoS 2 under the action of a vulcanizing agent to obtain the submerged super-amphiphobic oil-water separation material. The material prepared by the method has the beneficial effects that the material has excellent submerged super-amphiphobic characteristic, is super-oleophobic under water and super-hydrophobic under oil, can efficiently separate light oil/water and heavy oil/water mixtures, and has the separation efficiency of more than 90 percent. Has wide application prospect in the field of complex oil-water separation.

Inventors

CHEN YUQIANG
CHEN YANG
LI XIAOJUN
LI RENZHONG
JIANG GUOCE
LIU DONGJIE
DUAN ZONGFAN

Assignees

西安西热水务环保有限公司
西安工程大学
陕西艾克赛勒特新材料科技有限公司

Dates

Publication Date: 20260505
Application Date: 20251017

Claims (10)

1. The preparation method of the submerged super-amphiphobic oil-water separation material is characterized by comprising the following steps of: (1) Performing photoresist removal, acidification and vacuum plasma pretreatment on the carbon fiber; (2) Coating and growing Co (OH) 2 nanocrystalline on the surface of the pretreated carbon fiber, and calcining to convert Co (OH) 2 into Co 3 O 4 ; (3) Under the action of a vulcanizing agent, in-situ converting Co 3 O 4 on the surface of the carbon fiber obtained in the step (2) into CoS 2 to obtain the submerged super-amphiphobic oil-water separation material.
2. The preparation method of the submerged super-amphiphobic oil-water separation material according to claim 1, wherein in the step (1), the photoresist removing treatment step comprises the steps of soaking the carbon fiber in acetone, and drying after the soaking is finished; preferably, the carbon fiber is soaked in acetone at a soaking temperature of 20-30 ℃ for 1-4 hours; preferably, the temperature of the drying is 20-100 ℃, and the drying time is 1-8 hours; And/or the acidification step comprises the steps of soaking the photoresist-removed carbon fiber in concentrated nitric acid, washing the carbon fiber to be neutral by adopting water after the soaking is finished, and drying, wherein the soaking temperature of the carbon fiber soaked in the concentrated nitric acid is preferably 20-30 ℃, the soaking time period is 3-7 hours, the drying temperature is preferably 20-100 ℃, the drying time is 1-8 hours, and the mass concentration of the concentrated nitric acid is preferably 60-68%; And/or the vacuum degree of the vacuum plasma treatment is 10-60Pa, the power of the vacuum plasma treatment is 50-300W, and the duration of the vacuum plasma treatment is 5-30min.
3. The preparation method of the submerged super-amphiphobic oil-water separation material according to claim 1, wherein in the step (2), co (OH) 2 nanocrystalline is coated and grown on the surface of the pretreated carbon fiber, and the preparation method comprises the steps of carrying out contact reaction on the carbon fiber and cobalt salt reaction liquid, washing the reaction product with water and ethanol in sequence after the reaction is finished, and drying.
4. The method for preparing the submerged super-amphiphobic oil-water separation material according to claim 3, wherein the cobalt salt reaction solution comprises cobalt salt, an alkali source, a morphology regulator and water; Preferably, the cobalt salt comprises one or more of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetate; preferably, the alkali source comprises one or more of urea, ammonia and hexamethylenetetramine; Preferably, the morphology modifier comprises ammonium fluoride and/or ammonium bifluoride; preferably, the molar ratio of cobalt salt, alkali source, morphology regulator and water in the cobalt salt reaction solution is 1 (2-10): (2.5-10): (278-1111).
5. The preparation method of the submerged super-amphiphobic oil-water separation material according to claim 3, wherein the contact reaction temperature of the carbon fiber and the cobalt salt reaction solution is 90-150 ℃, and the contact reaction time is 6-12h.
6. The method for preparing a submerged super-amphiphobic oil-water separation material according to claim 1, wherein in the step (2), the temperature of the calcination treatment is 300-400 ℃, and the time of the calcination treatment is 1-6h; and/or the temperature rising rate in the calcination treatment process is 2-10 ℃ per minute; And/or the calcining atmosphere is air or oxygen.
7. The method for preparing a submerged super-amphiphobic oil-water separation material according to claim 1, wherein in the step (3), the vulcanizing agent comprises one or more of sodium sulfide, sodium hydrosulfide, ammonium sulfide, thiourea and thioacetamide; And/or, in the step (3), the step of converting Co 3 O 4 on the surface of the carbon fiber into CoS 2 comprises the step of contacting the carbon fiber obtained in the step (2) with a vulcanizing agent solution for vulcanization reaction.
8. The method for preparing a submerged super-amphiphobic oil-water separation material according to claim 7, wherein the concentration of the vulcanizing agent solution is 0.05-0.5mol/L; and/or the mass ratio of the carbon fiber to the vulcanizing agent is 1:0.8-5.6; and/or the temperature of the vulcanization reaction is 120-200 ℃, and the time of the vulcanization reaction is 10-24h.
9. The submerged super-amphiphobic oil-water separation material is characterized by being prepared by the preparation method of any one of claims 1-8.
10. The use of the submerged super-amphiphobic oil-water separation material obtained by the preparation method of any one of claims 1 to 8 or the submerged super-amphiphobic oil-water separation material of claim 9 in the treatment of oily wastewater and petroleum leakage.

Description

Submerged super-amphiphobic oil-water separation material and preparation method and application thereof Technical Field The application belongs to the technical field of oil-water mixture separation materials, and particularly relates to a submerged super-amphiphobic oil-water separation material, and a preparation method and application thereof. Background While industrial production is vigorously developed, the discharge amount of oily wastewater is rapidly increased, petroleum leakage accidents frequently occur, and serious threat is brought to ecological environment and human health. In order to solve the problem of treatment of oily wastewater, a plurality of technical means are developed, and the membrane separation technology is favored in the field of oil-water separation by virtue of the advantages of high efficiency, low energy consumption, simple and convenient operation and the like. However, most of the separation materials used in the current membrane separation technology are single-function, such as super-hydrophilic-super-oleophobic 'water removal' membranes are only suitable for light oil/water mixture separation, while super-hydrophilic-super-hydrophobic 'oil removal' membranes can only cope with heavy oil/water systems, which makes the application of the membrane separation materials in complex oil-water separation environments difficult. Therefore, researchers put forward the concept of super-amphiphobic under water, and the separation on demand is realized by pre-wetting regulation and control by letting the material super-oleophobic under water and super-hydrophobic under oil. However, the reported submerged super-amphiphobic materials are mostly modified by fluorine-containing compounds or rely on external stimuli (such as temperature, pH value, illumination and the like) to obtain super-amphiphobic characteristics, so that the cost is high, the environmental compatibility is poor, the response condition is harsh, the mechanical stability and the circulation performance are poor, and the application in complex oil-water separation environments is difficult. Disclosure of Invention The application provides a submerged super-amphiphobic oil-water separation material and a preparation method and application thereof, and aims to solve the problems of complex preparation process, high cost, poor stability and the like of the existing submerged super-amphiphobic material so as to realize efficient and stable separation of oily wastewater. The application provides a preparation method of a submerged super-amphiphobic oil-water separation material, which comprises the following steps of: (1) Performing photoresist removal, acidification and vacuum plasma pretreatment on the carbon fiber; (2) Coating and growing Co (OH) 2 nanocrystalline on the surface of the pretreated carbon fiber, and calcining to convert Co (OH) 2 into Co 3O4; (3) Under the action of a vulcanizing agent, in-situ converting Co 3O4 on the surface of the carbon fiber obtained in the step (2) into CoS 2 to obtain the submerged super-amphiphobic oil-water separation material. According to some embodiments of the preparation method of the submerged super-amphiphobic oil-water separation material, in the step (1), the photoresist removing treatment step comprises the steps of soaking the carbon fibers in acetone, and drying after the soaking is finished. According to some embodiments of the preparation method of the submerged super-amphiphobic oil-water separation material, the soaking temperature of the carbon fiber in acetone is 20-30 ℃, and the soaking time period is 1-4h. According to some embodiments of the preparation method of the submerged super-amphiphobic oil-water separation material, the drying temperature is 20-100 ℃, and the drying time is 1-8h. According to some embodiments of the preparation method of the submerged super-amphiphobic oil-water separation material, the acidification treatment step comprises the steps of soaking the carbon fiber after photoresist removal in concentrated nitric acid, washing the carbon fiber to be neutral by water after the soaking is finished, and drying, wherein as a preferable embodiment, the soaking temperature of the carbon fiber in the concentrated nitric acid is 20-30 ℃, and the soaking time is 3-7h. According to some embodiments of the preparation method of the submerged super-amphiphobic oil-water separation material, the drying temperature is 20-100 ℃, and the drying time is 1-8h. According to some embodiments of the preparation method of the submerged super-amphiphobic oil-water separation material, the mass concentration of the concentrated nitric acid is 60% -68%. According to some embodiments of the preparation method of the submerged super-amphiphobic oil-water separation material, the vacuum degree of the vacuum plasma treatment is 10-60Pa, the power of the vacuum plasma treatment is 50-300W, and the duration of the vacuum plasma treatment is 5-30min. According to so