CN104512942A - Method utilizing polylactic acid/carbon nanotube composite electro-spun fiber membrane to absorb and remove perfluorooctane sulfonate in water - Google Patents
Method utilizing polylactic acid/carbon nanotube composite electro-spun fiber membrane to absorb and remove perfluorooctane sulfonate in water Download PDFInfo
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/44—Materials comprising a mixture of organic materials
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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Abstract
The invention belongs to the field of sewage processing, and specifically relates to a method utilizing a polylactic acid/carbon nanotube composite electro-spun fiber membrane to absorb and remove perfluorooctane sulfonate in water. The method comprises two steps: preparation of a polylactic acid/carbon nanotube composite electro-spun fiber membrane and removal of perfluorooctane sulfonate in water through adsorption of the polylactic acid/carbon nanotube composite electro-spun fiber membrane. More specifically, the method comprise the following steps: taking polylactic acid and carbon nanotubes, which have been processed by acid, as the raw materials, then spinning the raw materials through an electrostatic spinning technology so as to obtain polylactic acid/carbon nanotube composite electro-spun fiber membrane, and then making the composite electro-spun fiber membrane carry out reactions with perfluorooctane sulfonate water solutions with different concentrations so as to remove perfluorooctane sulfonate in water through adsorption. The invention provides an efficient method for remove perfluorooctane sulfonate in water through adsorption, more than 70% of perfluorooctane sulfonate in water can be removed ( in a concentration range of 2-1000 microgram/liter), and the absorbent has the advantages of simple preparation, environment-friendliness, and easy recycling. The method is easy to operate, is economic and efficient, and will not generate secondary pollution to the environment.
Description
Technical field
The invention belongs to sewage treatment area, especially pollute the process field of sewage about Perfluorooctane sulfonates, be specially a kind of method utilizing Perfluorooctane sulfonates in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water.
Background technology
Perfluorooctane sulfonates (PFOS) is the high fluorine cpd of a class synthetic, possesses the characteristics such as hydrophobic, oleophobic simultaneously, is widely used in producing the surface soiling treatment agents such as textiles, leatherware, furniture and carpet; Because its chemical property is highly stable, be also used for the production field of many civilian and Industrial products such as coating, fire foam, floor polisher, agricultural chemicals and imaging material as intermediate.Due to the perfluor chemical structure that PFOS is special, cause it to boil for a long time in strong acid solution also can not be degraded, and the migration of the long distance of energy and transhipment, easily produce accumulation in vivo by food chain, metabolism of fat and mitochondrial obstacle can be caused, there is the multiple toxicity such as liver, fetal development, reproduction and nerve.Therefore, PFOS is considered to the new toxic organic pollutant of a class, is listed in the row of Some Persistent Organic Pollutants Black List by EPA, causes the very big concern of various countries environmentalist.
Since calendar year 2001 Kannan and Giesy etc. detects PFOS in the wildlife body of polar region, the world's ecosystems environment and comprise the mankind all organisms in all extensively there is PFOS and pollute.Environmental surveys finds, PFOS is widely distributed in water surrounding, is all detected in the surface water and tap water of world many countries.Show the analysis and research of external fresh water pollution situation, polluting is the most seriously Etobicoke river, Toronto, and PFOS concentration is up to 2.2 × 10
6ng/L, this is mainly because once by the pollution of being fluorine-containing fire foam before this sampling point.Nobuyoshi etc. study discovery, marine site, Eastern Pacific, marine site, the central and north, the Atlantic Ocean, marine site, Labrador, marginal basins marine site, Su Lu marine site, and Korea S, Japan, all having PFOS to detect in coastal marine site, China's Mainland, concentration range is often liter of tens to several thousand piks.The PFOS concentration range detected in the water samples such as Chinese the Changjiang river, the Zhujiang River and Song Hua River is respectively 0.01 ~ 14ng/L, 0.9 ~ 99ng/L and 0.06 ~ 8.04ng/L.Gold one and etc. detect in Tap Water from Some Cities, the surface water, underground water and the seawater samples such as China Liaoning, Beijing, Shanghai, Shandong, Jilin and Gansu all containing PFOS, in the surface water of enumeration district (ED), PFOS concentration range is 0.41 ~ 4.20ng/L, and mean concns is 2.07ng/L; Underground water and Dalian Area, Bohai Sea Gulf phosphorus FOS mean concns are respectively 1.61ng/L and 0.83ng/L.These results of study show, and the water body in the whole world all receives the pollution of PFOS.Although the concentration of PFOS in water is very low, because its residence time in water body is long, have accumulative, great threat is caused to aquatic ecosystem human health of unifying.Along with becoming increasingly conspicuous of water body PFOS pollution problem, people also recognize importance and the urgency of the middle PFOS that purifies waste water gradually.Therefore, how administering PFOS in water fast and effectively and pollute, purification, environmental protect, thus safeguard human health, is one of current significant challenge faced of environmentalist.
In recent years, Chinese scholars has carried out a large amount of research work to the pollutant abatement technology of PFOS, and the Treatment process related to mainly comprises physisorphtion, photocatalytic method, direct photolysis method, high temperature pyrolysis, sonochemistry method, microwave method and the mechanical method of residues etc.Because fluorine has very large electronegativity (-4.0), make carbon fluorine (C-F) key have strong polarity and be one of the maximum covalent linkage of occurring in nature bond energy (the about 110kcal/mol of bond energy).The stability that this chemical structure feature makes PFOS molecule is very strong, even if be also difficult to be degraded under the metabolism of stronger heating, illumination, chemical action, microbial process and higher vertebrate.Therefore, by contrast, absorption method is the technology of PFOS in a kind of high-efficient purification water.The key of adsorption method for purifying pollutent is utilized to be the selection of sorbent material.The special construction of carbon nanotube determines that it has unique physics-chem characteristic, and modifiability is strong; Huge specific surface area makes it have excellent absorption property to toxic organic pollutants such as PFOS, and therefore it is by as a kind of novel sorbent material.But carbon nanotube, usually in powder or particulate state, causes it to be difficult to reclaim from water after absorption, bring processing costs thus high or there is the problems such as secondary pollution risk.In addition, due to the nano-scale structure of carbon nanotube, make it have certain toxic effect to biology, cause the environmental behaviour of himself also to have risk.Increasing research report shows, the environmental risk of exposure is not only relevant with the characteristic of carbon nanotube inherence with toxicological effect, also relevant with the toxic pollutant being adsorbed on its surface.Therefore, carbon nanotube is subject to a definite limitation as sorbing material in the process application of actual PFOS polluted water.Therefore, how effectively to play the clear superiority of carbon nanotube adsorption performance, overcome the shortcomings such as it is difficult to be separated, less economical, contaminate environment, research and develop novel efficient adsorption purification techniques, for the purification of PFOS in water, there is important theory significance and using value.
High-voltage electrostatic spinning technology is a kind of new technique preparing nano fibrous membrane.This technology utilize charged polymers soln or melt in electrostatic field jet to realize the processing of superfine fibre film, little 1 ~ 2 order of magnitude of general fibre diameter that obtained Fibre diameter is prepared than traditional method, voidage is high, specific surface area is large, compact structure and have certain physical strength.Electrospun fiber membrane is also used as a kind of sorbent material efficiently, can realize, to the Adsorption rapidly and efficiently of hydrophobic organic pollutant in water, being easy to Separation and Recovery from water simultaneously, can not causing secondary pollution.But because PFOS has hydrophobic oleophobic characteristic, electrospun fiber membrane is undesirable to its adsorption efficiency.If by the feature that electrostatic spinning technique is adjustable flexibly, this technology is used to be fixed on electrospinning fibre by carbon nanotube, prepare polymer/carbon nano-tube composite electrospun tunica fibrosa, be expected to take into account efficient adsorption to be separated with simple and easy, significantly improve carbon nanotube and the electrospun fiber membrane practicality in ambient water process field.
Summary of the invention
A kind of efficient adsorption is the object of the present invention is to provide to remove the method for PFOS in water, namely using the poly(lactic acid) utilizing electrostatic spinning technique to prepare/carbon nanotube composite electrospun tunica fibrosa as sorbent material, the efficient adsorption to PFOS can be realized, reach the object removing PFOS in water.The sorbent material that the method adopts has that absorption property is good, environmental friendliness, preparation process simple, be easy to the advantages such as recycling; And method processing ease, high efficiency and time conservation.
Technical scheme of the present invention is:
In Adsorption water provided by the invention, the method for PFOS is for sorbent material starting material with biodegradable poly-lactic acid in high molecular weight and the stronger carbon nanotube of hydrophobicity, prepare poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa by electrostatic spinning technique, then this composite cellulosic membrane is used for the PFOS in Adsorption water.This efficient adsorption is removed the method for PFOS in water and is comprised two steps: the preparation of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and utilize PFOS in its Adsorption water.
The preparation process of wherein poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa comprises:
1) by molecular weight be 100,000 particles of polylactic acid be dissolved in methylene dichloride, stir after 3h and obtain clear gel solution, wherein the mass concentration of poly(lactic acid) is 13%;
2) taking 50mg through the carbon nanotube of acidification adds in 5mL methylene dichloride, and in numerical control ultrasonic apparatus under 20kHz condition ultrasonic 10min, make even carbon nanotube be scattered in methylene dichloride, obtain carbon nanotube-methylene dichloride dispersion liquid;
3) to step 1) in add the carbon nanotube-methylene dichloride dispersion liquid of certain volume in gained clear gel solution, and be placed on vortex mixer and mix 5min (1000rpm), more ultrasonic 10min (20kHz) makes uniform mixed gel;
4) by step 3) in gained mixed gel be incorporated in high-voltage electrostatic spinning device, regulate each parameter to obtain the injection of steady and continuous, in spinning whole process all with infrared lamp irradiation, volatilize completely to make methylene dichloride;
5) on the aluminium foil of dash receiver, collect poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa, treat that tunica fibrosa thickness reaches 0.5 ~ 0.6mm after 1 ~ 2h, stop spinning, gained composite electrospun tunica fibrosa at room temperature stores for future use;
PFOS step in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water is utilized to comprise:
A) gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is cut into 1cm × 1cm dice, and it is peeled from aluminium foil; B) measure the certain density PFOS aqueous solution of 50mL in polypropylene Erlenmeyer flask, and add the poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa of 50 ~ 55mg wherein;
C) by step b) in mixed system 25 DEG C, oscillatory reaction under the condition of 150rpm, timing sampling also uses HPLC-MS instrument (HPLC-MS/MS, API3200, Applied Biosystems, the U.S.) determination and analysis is carried out to the PFOS in solution.
In the inventive method, the preparation process 3 of wherein poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa) in the mass ratio of poly(lactic acid) and carbon nanotube be 600:1.
Utilize PFOS step b in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water) described in PFOS concentration range be 2 ~ 1000 μ g/L;
Utilize PFOS step c in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water) described in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and the sorption reaction time of PFOS be 20h.
In Adsorption water provided by the invention, the method tool of PFOS has the following advantages:
1. sorbent material poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa preparation process of adopting of the method is simple, polylactic acid electrospinning fibre film can provide carrier for granular carbon nanotube, carbon nanotube add mechanical property and the absorption property that significantly can strengthen electrospun fiber membrane, make composite cellulosic membrane have good adsorption performance, environmental friendliness, be easy to the advantages such as recycling.
2. simple to operate with the method for PFOS in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water, mild condition, with low cost, be beneficial to quick arrangement especially.
3. poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa high adsorption capacity, the PFOS of different concns in water can be removed by efficient adsorption, and by the polymkeric substance of changing differing materials or add dissimilar, that carbon nanotube that is quantity realizes composite electrospun tunica fibrosa absorption property regulation and control.
Accompanying drawing explanation
Fig. 1 a is the scanning electron microscope image of the blank polylactic acid electrospinning fibre film not adding carbon nanotube; Fig. 1 b is the scanning electron microscope image of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa;
Fig. 2 is reaction blank polylactic acid electrospinning fibre film (blank film) and poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa (CNT-film) eliminating rate of absorption to the PFOS of different concns after 20 hours.
Embodiment
In Adsorption water provided by the invention, the method for PFOS comprises two steps: the preparation of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and utilize PFOS in its Adsorption water.
The preparation process of wherein poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa comprises:
1) by molecular weight be 100,000 particles of polylactic acid be dissolved in methylene dichloride, stir after 3h and obtain clear gel solution, wherein the mass concentration of poly(lactic acid) is 13%;
2) taking 50mg through the carbon nanotube of acidification adds in 5mL methylene dichloride, and in numerical control ultrasonic apparatus under 20kHz condition ultrasonic 10min, make even carbon nanotube be scattered in methylene dichloride, obtain carbon nanotube-methylene dichloride dispersion liquid;
3) to step 1) in add the carbon nanotube-methylene dichloride dispersion liquid of certain volume in gained clear gel solution, and be placed on vortex mixer and mix 5min (1000rpm), more ultrasonic 10min (20kHz) makes uniform mixed gel;
4) high-voltage electrostatic spinning apparatus is made up of DC high-voltage power supply, syringe pump, spinning nozzle and receiving trap; By step 3) in gained mixed gel be incorporated in high-voltage electrostatic spinning device, regulating power source voltage is 11kV, and setting spinning solution flow velocity is 1.5mL/h, and receiving range is 15cm, to obtain the injection of steady and continuous; Spinning process control temperature is 25 ± 1 DEG C, and humidity is about 40%, all irradiates with infrared lamp, volatilize completely to make methylene dichloride in spinning whole process;
5) on the aluminium foil of dash receiver, collect electrospun fiber membrane, treat that tunica fibrosa thickness reaches 0.5 ~ 0.6mm after 1 ~ 2h, stop spinning, gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa at room temperature stores for future use;
PFOS step in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water is utilized to comprise:
A) gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is cut into 1cm × 1cm dice, and it is peeled from aluminium foil; B) measure the certain density PFOS aqueous solution of 50mL in polypropylene Erlenmeyer flask, and add the poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa of 50 ~ 55mg wherein;
C) by step b) in mixed system 25 DEG C, oscillatory reaction under the condition of 150rpm, sample after reaction 20h and use HPLC-MS instrument (HPLC-MS/MS, API3200, Applied Biosystems, the U.S.) determination and analysis is carried out to the PFOS in solution.
In the inventive method, the preparation process 3 of wherein poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa) in the mass ratio of poly(lactic acid) and carbon nanotube be 600:1.
In the inventive method, the carbon nanotube used is multi-walled carbon nano-tubes, can obtain from material supplier; Multi-walled carbon nano-tubes is first carried out acidification by the present invention, is used further to prepare poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa; Concrete acidification step is: carbon nanotube is placed in sulfuric acid and nitric acid mixing solutions that volume ratio is 3:1, and at 50 DEG C, ultrasonic 3h under 20kHz condition, leave standstill 24h afterwards, then with deionized water rinsing until elutriant is neutrality, finally carbon nanotube is placed in vacuum environment dry, for subsequent use.
In the inventive method, the high-voltage electrostatic spinning device used is device well known in the art, it is made up of high-voltage DC power supply, syringe pump, spinning nozzle and receiving trap usually, and used unit such as high-voltage DC power supply, syringe pump, spinning nozzle and metal sheet receptor etc. can be obtained by relevant device supplier.
In the inventive method, the PFOS strength of solution scope of testing is 2 ~ 1000 μ g/L.
Embodiment 1
First by 3g molecular weight be 100,000 poly(lactic acid) add in the glass spinner flask filling 20g dichloromethane solution, mixing is placed on magnetic stirring apparatus stirs 3h at ambient temperature obtains clear gel solution.Taking 50mg through the multi-walled carbon nano-tubes of acidification adds in 5mL methylene dichloride, and in numerical control ultrasonic apparatus ultrasonic 10min under 20kHz condition, makes multi-walled carbon nano-tubes be dispersed in methylene dichloride, obtains carbon nanotube-methylene dichloride dispersion liquid.Then getting a certain amount of dispersion liquid adds in polymeric transparent gelating soln, and vortex mixer mixes 5min (1000rpm), more ultrasonic 10min makes uniform carbon nano-tube/polymer mixed gel.Mixed gel is introduced in the spinning nozzle of electrostatic spinning apparatus, setting spinning solution flow velocity is 1.5mL/h, and polar plate spacing is 15cm, and adjustment high-voltage power voltage is 11kV, obtain the injection stream of steady and continuous, and collect fiber product on the dash receiver being coated with aluminium-foil paper.Spinning process control temperature is 25 ± 1 DEG C, and humidity is about 40%, all irradiates with infrared lamp, volatilize completely to make methylene dichloride in whole process.After 1 ~ 2h, tunica fibrosa thickness reaches 0.5 ~ 0.6mm, stops spinning, namely obtains polymer/carbon nano-tube composite electrospun tunica fibrosa.For carrying out control experiment, the poly(lactic acid) clear gel solution not adding carbon nanotube being introduced electrostatic spinning apparatus simultaneously, under identical spinning condition, preparing blank polylactic acid electrospinning fibre film.By blank polylactic acid electrospinning fibre film and poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa at field emission scanning electron microscope (FESEM S-4800 field emission scanning electron microscope, Hitachi, Ltd) under carry out fiber morphology sign, result shows that two kinds of fiber morphology are all more even.The diameter of blank polylactic acid electrospinning fibre is at about 1 ~ 2 μm, and fiber surface is more smooth; Because carbon nanotube is to the enhancing of spinning solution electroconductibility, a diameter number magnitude less of the diameter of blank polylactic acid electrospinning fibre of poly(lactic acid)/carbon nanotube composite electrospun fiber, most of diameter is 50 ~ 100nm, carbon nanotube is fixed in electrospun fiber membrane with forms such as being wound around, interting or cross, and bending abnormity appears in fiber surface.
Gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is cut into 1cm × 1cm dice, and it is peeled from aluminium foil.Then take 50 ~ 55mg (about 3) poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and join the PFOS aqueous solution that 50mL concentration is 2 μ g/L; And mixed system is placed in 25 DEG C, oscillatory reaction under the condition of 150rpm, sample after reaction 20h and measure through HPLC-MS instrument (HPLC-MS/MS, API3200, Applied Biosystems, the U.S.).Meanwhile, react under the same conditions with blank polylactic acid electrospinning fibre film and test in contrast.Poly(lactic acid) in the method/carbon nanotube composite electrospun tunica fibrosa is 91.43% to the eliminating rate of absorption of PFOS, and the eliminating rate of absorption of blank polylactic acid electrospinning fibre film to PFOS is only 44.59%.
Embodiment 2
The preparation process of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is with embodiment 1.
Gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is cut into 1cm × 1cm dice, and it is peeled from aluminium foil.Then take 50 ~ 55mg (about 3) poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and join the PFOS aqueous solution that 50mL concentration is 10 μ g/L; And mixed system is placed in 25 DEG C, oscillatory reaction under the condition of 150rpm, sample after reaction 20h and measure through HPLC-MS instrument (HPLC-MS/MS, API3200, Applied Biosystems, the U.S.).Meanwhile, react under the same conditions with blank polylactic acid electrospinning fibre film and test in contrast.Poly(lactic acid) in the method/carbon nanotube composite electrospun tunica fibrosa is 89.33% to the eliminating rate of absorption of PFOS, and the eliminating rate of absorption of blank polylactic acid electrospinning fibre film to PFOS is only 39.65%.
Embodiment 3
The preparation process of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is with embodiment 1.
Gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is cut into 1cm × 1cm dice, and it is peeled from aluminium foil.Then take 50 ~ 55mg (about 3) poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and join the PFOS aqueous solution that 50mL concentration is 100 μ g/L; And mixed system is placed in 25 DEG C, oscillatory reaction under the condition of 150rpm, sample after reaction 20h and measure through HPLC-MS instrument (HPLC-MS/MS, API3200, Applied Biosystems, the U.S.).Meanwhile, react under the same conditions with blank polylactic acid electrospinning fibre film and test in contrast.Poly(lactic acid) in the method/carbon nanotube composite electrospun tunica fibrosa is 82.62% to the eliminating rate of absorption of PFOS, and the eliminating rate of absorption of blank polylactic acid electrospinning fibre film to PFOS is only 31.08%.
Embodiment 4
The preparation process of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is with embodiment 1.
Gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is cut into 1cm × 1cm dice, and it is peeled from aluminium foil.Then take 50 ~ 55mg (about 3) poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and join the PFOS aqueous solution that 50mL concentration is 500 μ g/L; And mixed system is placed in 25 DEG C, oscillatory reaction under the condition of 150rpm, sample after reaction 20h and measure through HPLC-MS instrument (HPLC-MS/MS, API3200, Applied Biosystems, the U.S.).Meanwhile, react under the same conditions with blank polylactic acid electrospinning fibre film and test in contrast.Poly(lactic acid) in the method/carbon nanotube composite electrospun tunica fibrosa is 77.35% to the eliminating rate of absorption of PFOS, and the eliminating rate of absorption of blank polylactic acid electrospinning fibre film to PFOS is only 24.24%.
Embodiment 5
The preparation process of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is with embodiment 1.
Gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is cut into 1cm × 1cm dice, and it is peeled from aluminium foil.Then take 50 ~ 55mg (about 3) poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and join the PFOS aqueous solution that 50mL concentration is 1000 μ g/L; And mixed system is placed in 25 DEG C, oscillatory reaction under the condition of 150rpm, sample after reaction 20h and measure through HPLC-MS instrument (HPLC-MS/MS, API3200, Applied Biosystems, the U.S.).Meanwhile, react under the same conditions with blank polylactic acid electrospinning fibre film and test in contrast.Poly(lactic acid) in the method/carbon nanotube composite electrospun tunica fibrosa is 70.97% to the eliminating rate of absorption of PFOS, and the eliminating rate of absorption of blank polylactic acid electrospinning fibre film to PFOS is only 18.86%.
Claims (4)
1. one kind utilizes the method for Perfluorooctane sulfonates in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water, it is characterized in that, comprise two steps: the preparation of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa and utilize Perfluorooctane sulfonates in its Adsorption water;
The preparation process of wherein poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa comprises:
1) by molecular weight be 100,000 particles of polylactic acid be dissolved in methylene dichloride, stir after 3h and obtain clear gel solution, wherein the mass concentration of poly(lactic acid) is 13%;
2) taking 50mg through the carbon nanotube of acidification adds in 5mL methylene dichloride, and in numerical control ultrasonic apparatus under 20kHz condition ultrasonic 10min, make even carbon nanotube be scattered in methylene dichloride, obtain carbon nanotube-methylene dichloride dispersion liquid;
3) to step 1) in add the carbon nanotube-methylene dichloride dispersion liquid of certain volume in gained clear gel solution, and be placed on vortex mixer and mix 5min (1000rpm), more ultrasonic 10min (20kHz) makes uniform mixed gel;
4) high-voltage electrostatic spinning apparatus is made up of DC high-voltage power supply, syringe pump, spinning nozzle and receiving trap; By step 3) in gained mixed gel be incorporated in high-voltage electrostatic spinning device, regulating power source voltage is 11kV, and setting spinning solution flow velocity is 1.5mL/h, and receiving range is 15cm, to obtain the injection of steady and continuous; Spinning process control temperature is 25 ± 1 DEG C, and humidity is about 40%, all irradiates with infrared lamp, volatilize completely to make methylene dichloride in spinning whole process;
5) on the aluminium foil of dash receiver, collect electrospun fiber membrane, treat that tunica fibrosa thickness reaches 0.5 ~ 0.6mm after 1 ~ 2h, stop spinning, gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa at room temperature stores for future use;
Perfluorooctane sulfonates step in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water is utilized to comprise:
A) gained poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa is cut into 1cm × 1cm dice, and it is peeled from aluminium foil;
B) measure the certain density Perfluorooctane sulfonates aqueous solution of 50mL in polypropylene Erlenmeyer flask, and add the poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa of 50 ~ 55mg wherein;
C) by step b) in mixed system 25 DEG C, oscillatory reaction under the condition of 150rpm, timing sampling also uses HPLC-MS instrument (HPLC-MS/MS, API3200, Applied Biosystems, the U.S.) determination and analysis is carried out to the Perfluorooctane sulfonates in solution.
2., according to a kind of method utilizing Perfluorooctane sulfonates in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water described in claim 1, it is characterized in that: the preparation process 3 of poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa) in the mass ratio of poly(lactic acid) and carbon nanotube be 600:1.
3. a kind of method utilizing Perfluorooctane sulfonates in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water according to claim 1, is characterized in that: utilize Perfluorooctane sulfonates step b in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water) described in PFOS concentration range be 2 ~ 1000 μ g/L.
4. a kind of method utilizing Perfluorooctane sulfonates in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water according to claim 1, is characterized in that: utilize Perfluorooctane sulfonates step c in poly(lactic acid)/carbon nanotube composite electrospun tunica fibrosa Adsorption water) described in sorption reaction time be 20h.
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| CN106694055A (en) * | 2016-11-26 | 2017-05-24 | 杭州同净环境科技有限公司 | Functional nano-composite material, preparation method and application thereof |
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| CN107486149A (en) * | 2017-08-15 | 2017-12-19 | 太原理工大学 | Carbon nano-tube film and preparation method and application |
| CN111330456A (en) * | 2020-03-05 | 2020-06-26 | 西南交通大学 | Biodegradable array composite membrane with selective permeation and preparation method thereof |
| CN111282556A (en) * | 2020-03-27 | 2020-06-16 | 神华神东煤炭集团有限责任公司 | Defluorination composite fiber membrane, preparation method and application thereof |
| CN111282556B (en) * | 2020-03-27 | 2023-03-28 | 神华神东煤炭集团有限责任公司 | Defluorination composite fiber membrane, preparation method and application thereof |
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