CN113073466A - Preparation method of super-hydrophobic diazonium fluoroborate/carbon composite fiber felt - Google Patents
Preparation method of super-hydrophobic diazonium fluoroborate/carbon composite fiber felt Download PDFInfo
- Publication number
- CN113073466A CN113073466A CN202110267870.5A CN202110267870A CN113073466A CN 113073466 A CN113073466 A CN 113073466A CN 202110267870 A CN202110267870 A CN 202110267870A CN 113073466 A CN113073466 A CN 113073466A
- Authority
- CN
- China
- Prior art keywords
- fiber felt
- oil
- composite fiber
- water
- trifluoromethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/81—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron; with boron halides; with fluoroborates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Abstract
The invention relates to the field of functional materials, in particular to a preparation method of a super-hydrophobic fluoboric acid diazonium salt/carbon composite fiber felt. The composite fiber felt can effectively separate an oil/water immiscible mixture, has high oil flux, rejection rate and water pressure resistance, has demulsification capacity on an oil-in-water emulsion, has good recycling performance in the oil-water separation process, can keep the characteristics in strong acid, strong alkali solution and corrosive solution, and has good thermal stability and flame retardance. The modified carbon fiber felt can effectively solve the problems of oil stain waste water discharge, crude oil leakage, black and odorous sewage treatment and the like due to the excellent characteristics, and has wide application prospect.
Description
Technical Field
The invention relates to the field of functional materials, in particular to a preparation method of a super-hydrophobic diazonium fluoroborate/carbon composite fiber felt.
Background
In recent years, crude oil leakage and sewage discharge are more and more serious worldwide, problems caused by the crude oil leakage and the sewage discharge such as ecological damage and seawater eutrophication are not ignored, and oil stain treatment is not slow enough. How to treat the sewage and effectively separate oil from water becomes an urgent task for human beings, and the 2010 oil leakage event in the gulf of mexico causes rivers and oceans to bear huge pollution loads, seriously damages the ecological balance of water areas, damages electric power systems and has no obvious significance on oil-water treatment. For oil spills and sewage discharges, common methods include: in-situ burning, chemical oil eliminating agent application and adsorbent (wool, active carbon, sulfonated coal, diatomite, coke, etc.), which are inefficient, expensive, even cause secondary pollution, need to be disposed again, and severely limit their application. In addition, the currently commonly used oil-absorbing felt still has the defect of low selective separation efficiency, namely, a large amount of water can be absorbed while absorbing oil, and the oil-water separation material is in urgent need of innovation.
The carbon fiber felt has three-dimensional porosity, stable chemical performance, broad adsorption spectrum and large capacity, has the adsorption capacity for organic steam such as gasoline, aldehydes, phenols, alcohols, olefins and the like which is several times to dozens of times larger than that of active carbon (GAC), has good adsorption for inorganic gas (such as No, N, HF, HCl and the like), and has potential application value in the field of oil-water separation. Due to the inherent hydrophobicity of the carbon fiber felt, the carbon fiber felt is difficult to perform functional modification, and the selective separation efficiency is low.
Therefore, how to further modify the carbon fiber felt to combine the characteristics of high selective separation efficiency, no acid and alkali, long cycle service life and flame retardancy is one of the problems to be solved in the field.
Disclosure of Invention
Aiming at various problems in the prior art, the invention provides a preparation method of a super-hydrophobic fluoboric acid diazonium salt/carbon composite fiber felt, which comprises the steps of preparing fluoboric acid diazonium salt by utilizing the replacement reaction of 4-trifluoromethyl diazobenzene hydrochloride aqueous solution and sodium fluoborate, dissolving the fluoboric acid diazonium salt in acetone, and compounding 4-trifluoromethyl phenyl with carbon fibers by utilizing the oleophylic characteristic of a carbon fiber felt matrix to obtain the composite fiber felt with the super-hydrophobic characteristic; the composite fiber felt can effectively separate an oil/water immiscible mixture, has high oil flux, rejection rate and water pressure resistance, has demulsification capacity on an oil-in-water emulsion, has good recycling performance in the oil-water separation process, can keep the characteristics in strong acid, strong alkali solution and corrosive solution, and has good thermal stability and flame retardance. The modified carbon fiber felt can effectively solve the problems of oil stain waste water discharge, crude oil leakage, black and odorous sewage treatment and the like due to the excellent characteristics, and has wide application prospect.
The applicant previously filed for 4-trifluoromethyl aniline as a raw material to prepare corresponding 4-trifluoromethyl diazobenzene hydrochloride under the action of hydrochloric acid and sodium nitrite, and a carbon fiber felt is subjected to UV-O3The preparation method comprises the following steps of treating, preparing the UV-carbon fiber felt, and then reacting with 4-trifluoromethyl diazobenzene hydrochloride to prepare the fluorinated-UV-carbon fiber felt, wherein the technical scheme can also obtain a good hydrophobic effect, but hydrophilic treatment is required during processing, so that the preparation time and cost are further increased, and the inventor provides a brand-new technical scheme of the application through research, wherein the specific technical scheme is as follows:
a preparation method of a super-hydrophobic diazonium fluoroborate/carbon composite fiber felt comprises the following specific steps:
(1) dissolving 6.15g (0.56mol) of sodium fluoroborate in 7.81mL of water, keeping the temperature below 5 ℃, adding the sodium fluoroborate into a three-neck flask containing 0.04mol of 4-trifluoromethyl diazobenzene hydrochloride solution with the mass fraction of 95% under the stirring state, keeping the temperature below 5 ℃, and finishing the preparation of 4-trifluoromethyl diazobenzene tetrafluoroborate (referred to as diazonium fluoroborate) when a large amount of orange yellow precipitate is generated;
in the reaction process, the molar ratio of the sodium fluoborate to the 4-trifluoromethyl diazobenzene hydrochloride is 14: 1.
(2) Sequentially washing the carbon fiber felt with acetone, ethanol and deionized water for 2 hours respectively, and drying in a forced air drying oven for later use;
(3) respectively preparing diazonium fluoroborate acetone solutions with the concentrations of 5mg/mL, 10mg/mL, 15mg/mL and 20mg/mL, respectively putting the prepared carbon fiber felt in the step (2) into the diazonium acetone solutions with different concentrations, and reacting for 12 hours at room temperature. Finally, cleaning the carbon fiber felt with acetone and ultrapure water for three times respectively to obtain a diazonium salt acetone solution modified carbon fiber felt;
through tests, in industrial application, the optimal concentration of the 4-trifluoromethyl diazobenzene tetrafluoroborate acetone solution is 10mg/ml, and the dosage of each reagent is enlarged in a same ratio during specific operation.
According to the preparation method, 4-trifluoromethyl diazobenzene hydrochloride aqueous solution and sodium fluoborate are subjected to a displacement reaction to prepare the diazonium fluoborate, then the diazonium fluoborate is dissolved in acetone, and finally 4-trifluoromethyl diazobenzene and carbon fibers are compounded by using the oleophylic property of a carbon fiber felt matrix to prepare the composite fiber felt with the super-hydrophobic property, so that the preparation method is simple and rapid to operate and low in cost; after the 4-trifluoromethylphenyl functional group contained in the diazonium fluoroborate acetone solution is grafted on the surface of the carbon fiber by the diazo chemical method in the step (3), the effect of reducing the surface energy is achieved, and the surface of the prepared diazonium fluoroborate/carbon composite fiber felt has super-hydrophobic/super-oleophilic characteristics, so that the diazonium fluoroborate/carbon composite fiber felt has effective oil-water separation characteristics;
in contrast to the earlier applications of the present application, UV-O is not used in the present application3The treatment is carried out by selecting sodium fluoborate and acetone, so that the step of hydrophilic treatment is saved, the operation is simpler and more convenient, and the treatment time is obviousThe method is shortened and is more suitable for industrial application;
meanwhile, the carbon fiber felt has a three-dimensional porous structure and high porosity, so the carbon fiber felt has strong adsorption capacity, can absorb various oils, has strong adsorption to various organic solvents, has the adsorption capacity which can reach 4-14 times of the self weight, and has stable physical and chemical properties and long cycle service life, and the oil absorption capacity is not obviously changed after being recycled for ten times; the finally prepared super-hydrophobic diazonium fluoroborate/carbon composite fiber felt has good flame retardance, and organic matters and oil products are inflammable and explosive, so that the super-hydrophobic diazonium fluoroborate/carbon composite fiber felt can play a great role in treating organic matter emission and offshore oil spill accidents.
In summary, the composite fiber mat provided by the patent can effectively separate oil/water immiscible mixtures, has high oil flux, rejection rate and water pressure resistance, has demulsification capability on oil-in-water emulsions, has good recycling performance in the oil-water separation process, can maintain the characteristics of the oil-in-water emulsions in strong acid and strong alkali solutions and corrosive solutions, and has good thermal stability and flame retardance. The modified carbon fiber felt can effectively solve the problems of oil stain waste water discharge, crude oil leakage, black and odorous sewage treatment and the like due to the excellent characteristics, and has wide application prospect.
Drawings
FIG. 1 is a graphical representation of the results of the flame retardancy and thermal stability tests of the composite fiber mat obtained in example 1;
FIG. 2 is a schematic diagram of the super-hydrophobic property test result of the composite fiber mat obtained in example 1;
FIG. 3 is a graphical representation of the corrosion resistance test results for the composite fiber mat obtained in example 1;
FIG. 4 is a schematic representation of the cycle life test results for the composite fiber mat obtained in example 1;
FIG. 5 is a graphical representation of the demulsification test results obtained for the composite fiber mat of example 1.
Detailed Description
The present invention is further described below in conjunction with examples which will allow those skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1
A preparation method of a super-hydrophobic diazonium fluoroborate/carbon composite fiber felt comprises the following specific steps:
(1) dissolving 6.15g (0.56mol) of sodium fluoroborate in 7.81mL of water, keeping the temperature below 5 ℃, adding the sodium fluoroborate into a three-neck flask containing 0.04mol of 4-trifluoromethyl diazobenzene hydrochloride solution with the mass fraction of 95% under the stirring state, keeping the temperature below 5 ℃, and finishing the preparation of 4-trifluoromethyl diazobenzene tetrafluoroborate (referred to as diazonium fluoroborate) when a large amount of orange yellow precipitate is generated;
(2) sequentially cleaning the carbon fiber felt by using acetone, ethanol and deionized water for 2 hours respectively, putting the carbon fiber felt into a forced air drying oven for drying for later use, and then cutting the carbon fiber felt into small squares of 0.05 g;
(3) preparing a 10mg/mL diazonium fluoroborate acetone solution, respectively putting the prepared carbon fiber felt small blocks in the step (2) into 20mL diazonium salt acetone solutions with different concentrations, and reacting at room temperature for 12 h. And finally, cleaning the carbon fiber felt with acetone and ultrapure water for three times respectively to obtain the diazonium salt acetone solution modified carbon fiber felt.
The prepared diazonium salt acetone solution modified carbon fiber felt is subjected to related detection, and the result is as follows:
(1) flame retardancy and Heat stability test
The fluoboric acid diazonium salt/carbon composite fiber felt is soaked in alcohol for 2-3 minutes and is ignited after being taken out, as can be seen from figure 1, the fluoboric acid diazonium salt/carbon composite fiber felt is almost unchanged macroscopically before and after combustion, and an underwater contact angle after the combustion is measured can still reach 150.9 +/-0.4 degrees, which indicates that the fluoboric acid diazonium salt/carbon composite fiber felt has good flame retardance and thermal stability;
(2) super-hydrophobic property
By modifying the fluoboric acid diazonium salt/carbon composite fiber felt with low surface energy, the water contact angle of the composite fiber felt can reach 153.06 degrees +/-0.2 degrees, namely the composite fiber felt has super-hydrophobic characteristics; and can rapidly adsorb organic matters (chloroform) in water within 2s, which shows that the fluoboric acid diazonium salt/carbon composite fiber felt has the characteristic of effectively separating oil/water mixture (figure 2);
(3) corrosion resistance test
Preparing a solution with the pH value of 1-13 by using hydrochloric acid and ammonia water, then immersing the fluorinated carbon fiber felt into the solution for 30min under the action of external force, taking out the fluorinated carbon fiber felt, cleaning the fluorinated carbon fiber felt for 10min by using ultrapure water, and placing the cleaned fluorinated carbon fiber felt into a forced air drying oven for drying. Then testing the water contact angle of the carbon fiber felt, wherein the result is shown in figure 3, and after the carbon fiber felt is soaked in a solution with the pH value of 5-9, the water contact angle is still larger than 150 degrees, so that the carbon fiber felt shows a super-hydrophobic characteristic; after the coating is soaked in a solution with a pH value within other ranges, the water contact angle is still larger than 140 degrees, and the coating shows better corrosion resistance;
(4) cycle life
Organic matters adsorbed by the fluoboric acid diazonium salt/carbon composite fiber felt are removed through extrusion and vibration, then the organic matters are dried for reuse, and the adsorption performance of the organic matters on various organic matters is not reduced after the organic matters are recycled for at least 10 times, which shows that the composite fiber felt has good recycling service life (the result is shown in figure 4);
(5) demulsification test
First, V (water) is prepared: the method comprises the steps of mixing oil (toluene, cyclohexane and hexadecane) with V (oil): 9:1, preparing an oil-in-water emulsion by ultrasonic treatment for 1 hour and shaking for 1 hour, putting a fluorine-boric acid diazonium salt/carbon composite fiber felt into the prepared oil-in-water emulsion, and performing demulsification under stirring in the whole process, wherein oil droplets almost completely disappear after demulsification, and the liquid becomes clear from turbidity, so that the composite fiber felt has strong demulsification capability on the oil-in-water emulsion (fig. 5, wherein a toluene-in-water emulsion, a cyclohexane-in-water emulsion and a hexadecane-in-water emulsion are sequentially formed from top to bottom in fig. 5, the left side is the liquid morphology before demulsification, and the right side is the liquid morphology after demulsification, which is obtained by observation.
Example 2
A preparation method of a super-hydrophobic diazonium fluoroborate/carbon composite fiber felt comprises the following specific steps:
(1) 76.88g (7mol) of sodium fluoborate is dissolved in 97.63mL of water, the temperature is kept below 5 ℃, 0.5mol of 4-trifluoromethyl diazobenzene hydrochloride solution with the mass fraction of 95% is added into a three-neck flask with stirring, the temperature is kept below 5 ℃, and when a large amount of orange yellow precipitate is generated, the preparation of 4-trifluoromethyl diazobenzene tetrafluoroborate (referred to as diazonium fluoborate for short) is finished;
(2) sequentially cleaning the carbon fiber felt by using acetone, ethanol and deionized water for 2 hours respectively, putting the carbon fiber felt into a forced air drying oven for drying for later use, and then cutting the carbon fiber felt into small squares of 0.05 g;
(3) preparing a 10mg/mL diazonium fluoroborate acetone solution, respectively putting the prepared carbon fiber felt small blocks in the step (2) into 20mL diazonium salt acetone solutions with different concentrations, and reacting at room temperature for 12 h. And finally, cleaning the carbon fiber felt with acetone and ultrapure water for three times respectively to obtain the diazonium salt acetone solution modified carbon fiber felt.
Performing related detection on the carbon fiber felt modified by the diazonium salt acetone solution prepared by adding water, wherein the result shows that the obtained fluoboric acid diazonium salt/carbon composite fiber felt has flame retardance and thermal stability; the water contact angle can reach 151.04 degrees +/-0.6 degrees, and the super-hydrophobic oil-water separation device has super-hydrophobic characteristics and can effectively separate oil/water mixtures; after the coating is soaked in a solution with the pH value of 1-13 for half an hour, the water contact angle is still larger than 150 degrees, and the coating shows better corrosion resistance; after the composite material is recycled for at least 10 times, the adsorption performance of the composite material on various organic matters is basically kept unchanged, and the composite material has good recycling service life; and has strong demulsifying capability to oil-in-water emulsions.
Example 3
A preparation method of a super-hydrophobic diazonium fluoroborate/carbon composite fiber felt comprises the following specific steps:
(1) dissolving 6.15Kg (560mol) of sodium fluoroborate in 7.81L of water, keeping the temperature below 5 ℃, adding 40mol of 4-trifluoromethyl diazobenzene hydrochloride solution with the mass fraction of 95% into a three-neck flask with stirring, keeping the temperature below 5 ℃, and completing the preparation of 4-trifluoromethyl diazobenzene tetrafluoroborate (referred to as diazonium fluoroborate) when a large amount of orange precipitate is generated;
(2) sequentially washing the carbon fiber felt with acetone, ethanol and deionized water for 2 hours respectively, and drying in a forced air drying oven for later use;
(3) preparing a 10g/L diazonium fluoroborate acetone solution, putting the prepared carbon fiber felt in the step (2) into 20L of the diazonium salt acetone solution with the concentration, and reacting for 12h at room temperature. And finally, cleaning the carbon fiber felt with acetone and ultrapure water for three times respectively to obtain the diazonium salt acetone solution modified carbon fiber felt.
After the amplification process of this embodiment is adopted, the prepared diazonium salt acetone solution modified carbon fiber felt is subjected to related detection, and the results are as follows:
(1) flame retardancy and Heat stability test
Dipping the fluoboric acid diazonium salt/carbon composite fiber felt in alcohol for 2-3 minutes, taking out and igniting, wherein the fluoboric acid diazonium salt/carbon composite fiber felt is almost unchanged macroscopically before and after combustion, and an underwater contact angle after the combustion can still reach 151.2 +/-0.5 degrees, which indicates that the fluoboric acid diazonium salt/carbon composite fiber felt has good flame retardance and thermal stability;
(2) super-hydrophobic property
By modifying the fluoboric acid diazonium salt/carbon composite fiber felt with low surface energy, the water contact angle of the composite fiber felt can reach 152.04 degrees +/-0.8 degrees, namely the composite fiber felt has super-hydrophobic characteristics; organic matters (such as chloroform, toluene, dichloromethane and the like) in water can be rapidly adsorbed within 2s, which shows that the fluoboric acid diazonium salt/carbon composite fiber felt has the characteristic of effectively separating oil/water mixture;
(3) corrosion resistance test
Preparing a solution with the pH value of 1-13 by using hydrochloric acid and ammonia water, then soaking the fluorinated carbon fiber felt into the solution under the action of external force for 35min, taking out, washing with ultrapure water for 15min, and drying in a forced air drying oven. Then testing the water contact angle of the carbon fiber felt, and after soaking in a solution with the pH value of 6-10, the water contact angle is still larger than 150 degrees, so that the super-hydrophobic characteristic is shown; after the coating is soaked in a solution with a pH value within other ranges, the water contact angle is still larger than 140 degrees, and the coating shows better corrosion resistance;
(4) cycle life
Organic matters adsorbed by the fluoboric acid diazonium salt/carbon composite fiber felt are removed through extrusion and vibration, then the organic matters are dried for reuse, and the adsorption performance of the organic matters on various organic matters is basically kept unchanged after the organic matters are recycled for at least 10 times, which shows that the composite fiber felt has good recycling service life;
(5) demulsification test
First, V (water) is prepared: the method comprises the steps of mixing oil (chloroform, dichloroethane and toluene) with water, preparing an oil-in-water emulsion by ultrasonic treatment for 1.5h and shaking for 1.5h, putting a fluorine-boric acid diazonium salt/carbon composite fiber felt into the prepared oil-in-water emulsion, and performing demulsification under stirring in the whole process, wherein small oil drops almost completely disappear after the demulsification, and the liquid becomes clear from turbidity, which shows that the composite fiber felt has strong demulsification capability on the oil-in-water emulsion.
Therefore, after the process is amplified, the technical scheme of the invention has still obvious effect and stronger industrial practicability.
Comparative example
A preparation method of a modified carbon fiber felt for oil-water separation comprises the following specific steps:
(1) and cleaning the carbon fiber felt with acetone, ethanol and deionized water in sequence, and drying in a forced air drying oven. And (3) treating the carbon fiber felt for 15-45 minutes by using a UV-ozone cleaning machine to obtain the UV-carbon fiber felt.
(2) 3.2g of p-trifluoromethylaniline, 6mL of concentrated hydrochloric acid, and 6mL of deionized water were placed in a three-necked flask, and the temperature was raised to 60 ℃ to sufficiently dissolve the p-trifluoromethyl group. Then cooling to below 5 ℃, dropwise adding a sodium nitrite solution, detecting by using a starch potassium iodide test paper, and when the test paper turns into blue, proving that the diazo reaction is finished and the 4-trifluoromethyl diazobenzene hydrochloride solution is generated.
(3) Dividing the UV-carbon fiber felt obtained in the step (1) into three groups of 0.1g, 0.2g and 0.3g, and respectively reacting with the 4-trifluoromethyl diazobenzene hydrochloride solution prepared in the step (2) for 3 hours to generate the fluorinated carbon fiber felt.
The 4-trifluoromethyl diazobenzene hydrochloride solution prepared in the step (2) must be prepared in situ, and the temperature needs to be kept below 5 ℃.
Compared with the comparative example, the processing method of the fluoroboric acid diazonium salt/carbon composite fiber felt provided by the invention does not need to carry out UV-ozone hydrophilic treatment, shortens the whole processing time of the carbon fiber felt by 1 hour, and simplifies the operation process.
Experiments show that the prepared fluoboric acid diazonium salt/carbon composite fiber felt can be effectively separated from an oil/water immiscible mixture, has high oil flux, rejection rate and water pressure resistance, has demulsification capability on an oil-in-water emulsion, has good recycling performance in the oil-water separation process, can keep the characteristics in strong acid and alkali solutions and corrosive solutions, and has good thermal stability and flame retardance. The performance of the fluorinated carbon fiber felt is basically similar to that of the fluorinated carbon fiber felt prepared by the comparative example, but the preparation process time is obviously shortened, and the fluorinated carbon fiber felt has better industrial application value.
Claims (4)
1. A preparation method of a super-hydrophobic diazonium fluoroborate/carbon composite fiber felt is characterized by comprising the following steps: the method comprises the following specific steps:
(1) dissolving sodium fluoborate in water, keeping the temperature below 5 ℃, adding the sodium fluoborate into a three-neck flask containing a 4-trifluoromethyl diazobenzene hydrochloride solution under a stirring state, keeping the temperature below 5 ℃, and finishing the preparation of the 4-trifluoromethyl diazobenzene tetrafluoroborate when a large amount of orange yellow precipitates are generated;
(2) sequentially washing the carbon fiber felt with acetone, ethanol and deionized water for 2 hours respectively, and drying in a forced air drying oven for later use;
(3) preparing 4-trifluoromethyl diazobenzene tetrafluoroborate acetone solutions with the concentrations of 5mg/mL, 10mg/mL, 15mg/mL and 20mg/mL respectively, putting the prepared carbon fiber felt small square blocks in the step (2) into 20mL of diazonium salt acetone solutions with different concentrations respectively, and reacting for 12 hours at room temperature. And finally, cleaning the carbon fiber felt with acetone and ultrapure water for three times respectively to obtain the diazonium salt acetone solution modified carbon fiber felt.
2. The method for preparing the superhydrophobic diazonium fluoroborate/carbon composite fiber felt according to claim 1, wherein the method comprises the following steps: the molar ratio of sodium fluoroborate to 4-trifluoromethyl diazobenzene hydrochloride is 14: 1.
3. The method for preparing the superhydrophobic diazonium fluoroborate/carbon composite fiber felt according to claim 1, wherein the method comprises the following steps: the mass fraction of the 4-trifluoromethyl diazobenzene hydrochloride solution is 95%.
4. The method for preparing the superhydrophobic diazonium fluoroborate/carbon composite fiber felt according to claim 1, wherein the method comprises the following steps: the concentration of the 4-trifluoromethyl diazobenzene tetrafluoroborate acetone solution in the step (3) is 10 mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110267870.5A CN113073466B (en) | 2021-03-12 | 2021-03-12 | Preparation method of super-hydrophobic diazonium fluoroborate/carbon composite fiber felt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110267870.5A CN113073466B (en) | 2021-03-12 | 2021-03-12 | Preparation method of super-hydrophobic diazonium fluoroborate/carbon composite fiber felt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113073466A true CN113073466A (en) | 2021-07-06 |
| CN113073466B CN113073466B (en) | 2022-10-21 |
Family
ID=76612668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110267870.5A Active CN113073466B (en) | 2021-03-12 | 2021-03-12 | Preparation method of super-hydrophobic diazonium fluoroborate/carbon composite fiber felt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113073466B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090181240A1 (en) * | 2007-12-07 | 2009-07-16 | Tenaris Connections Ag | Diazonium functionalized nanoparticles and methods for binding nanoparticles to metallic surfaces |
| CN110975332A (en) * | 2019-12-23 | 2020-04-10 | 中国石油大学(华东) | Carbon fiber felt modification method for oil-water separation |
-
2021
- 2021-03-12 CN CN202110267870.5A patent/CN113073466B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090181240A1 (en) * | 2007-12-07 | 2009-07-16 | Tenaris Connections Ag | Diazonium functionalized nanoparticles and methods for binding nanoparticles to metallic surfaces |
| CN110975332A (en) * | 2019-12-23 | 2020-04-10 | 中国石油大学(华东) | Carbon fiber felt modification method for oil-water separation |
Non-Patent Citations (2)
| Title |
|---|
| 张龙: "《超疏水表面的制备、结构与性能研究》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 童志平等: "《双偶氮生色开链冠醚的合成》", 《西南交通大学学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113073466B (en) | 2022-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104610728B (en) | A kind of graphene oxide polyurethane composite foam and its production and use | |
| Li et al. | One-pot room-temperature synthesis of covalent organic framework-coated superhydrophobic sponges for highly efficient oil-water separation | |
| CN107159129B (en) | One-step preparation method and application of PDMS (polydimethylsiloxane) constructed super-hydrophobic melamine spongy carbon material | |
| CN103980530B (en) | A kind of preparation method of seaweed fiber element aerogel oil absorption material | |
| CN105399979A (en) | Oleophylic hydrophobic cellulose sponge and preparation method thereof | |
| CN109621923A (en) | A kind of super-hydrophobic oleophylic sponge material and preparation method thereof and water-oil separating application | |
| CN111001190B (en) | Preparation method and application of emulsion separation membrane with controllable wettability | |
| Zhang et al. | Robust, fluorine-free and superhydrophobic composite melamine sponge modified with dual silanized SiO2 microspheres for oil–water separation | |
| CN104725662A (en) | Lipophilic polyurethane sponge and preparation method thereof | |
| CN103881127A (en) | Preparation method of porous polybenzimidazole/phosphoric acid composite membrane | |
| CN113073466B (en) | Preparation method of super-hydrophobic diazonium fluoroborate/carbon composite fiber felt | |
| Ouyang et al. | 3D flexible superhydrophobic polyphosphazene coated melamine sponge for oil–water separation | |
| CN110314829A (en) | It is a kind of that oneself puts out a fire, the preparation method of super hydrophilic, underwater super oleophobic coating | |
| Zhang et al. | Continuous separation of oil from water surface by a novel tubular unit based on graphene coated polyurethane sponge | |
| CN107163573A (en) | A kind of halloysite nanotubes and polyaniline compound oil absorption material | |
| Tang et al. | Enhanced adsorption of methyl orange by vermiculite modified by cetyltrimethylammonium bromide (CTMAB) | |
| CN110975332A (en) | Carbon fiber felt modification method for oil-water separation | |
| Cao et al. | Functionalized carbon fiber felts with selective superwettability and fire retardancy: Designed for efficient oil/water separation | |
| CN107043275A (en) | Porous oil-absorbing ceramics that a kind of graphene is modified and preparation method thereof | |
| Gatou et al. | Commercial sponges as a novel technology for crude oil removal from seawater and industrial wastewater: A review | |
| Huang et al. | Popped rice biochar and superhydrophobic SiO 2/popped rice biochar for oil adsorption | |
| CN103611502A (en) | Preparation method of non-woven fabric petroleum adsorption bag coated with ZIF-8 adsorbent | |
| CN106893135A (en) | A kind of preparation method of the melamine foamed plastic oil absorption material that toughness improves | |
| CN111346480A (en) | Treatment device and treatment method for methanol waste gas | |
| CN106701299A (en) | Waste transformer insulating oil collection and recycling method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |