CN108940215B - Method for removing polycyclic aromatic hydrocarbon in enrichment manner - Google Patents
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- CN108940215B CN108940215B CN201810927445.2A CN201810927445A CN108940215B CN 108940215 B CN108940215 B CN 108940215B CN 201810927445 A CN201810927445 A CN 201810927445A CN 108940215 B CN108940215 B CN 108940215B
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 162
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Abstract
The invention relates to a method for removing polycyclic aromatic hydrocarbon in an enrichment way. The method comprises the following steps: step 1: synthesizing a polycyclic aromatic hydrocarbon adsorbent; the synthesized polycyclic aromatic hydrocarbon adsorbent is prepared by synthesizing Fe by using a hydrothermal method3O4Magnetic microsphere with Fe coated with dopamine3O4Magnetic microspheres are modified by a dimercapto compound to prepare a polycyclic aromatic hydrocarbon adsorbent; step 2: the polycyclic aromatic hydrocarbon adsorbent is rich in polycyclic aromatic hydrocarbon. The polycyclic aromatic hydrocarbon adsorbent is synthesized by a sulfydryl-alkene click chemistry method, is used for adsorbing polycyclic aromatic hydrocarbon, has high adsorption efficiency, is easy to separate, and can be separated only by a magnet.
Description
The application is divided into divisional applications based on an invention patent with the application date of 2016-08-01, the application number of 201610621741.0 and the name of 'a method for removing polycyclic aromatic hydrocarbon'.
Technical Field
The invention relates to a method for removing polycyclic aromatic hydrocarbon in an enrichment way.
Background
Polycyclic aromatic hydrocarbons are neutral or non-polar organic compounds containing two or more benzene rings or heterocycles arranged in linear, angular or cluster form, and exist in tobacco smoke, automobile exhaust, petrochemicals, and incompletely combusted organic compounds such as coal, wood, and oil. Can enter the human body through the food chain and respiration, and is enriched in the human body, thereby affecting gene expression and causing induction of cancer, mutagenicity, teratogenicity and other diseases, and has been listed as a priority for controlling pollutants by countries in the world.
The spirulina has the effects of resisting aging, resisting anoxia, resisting fatigue, resisting radiation, reducing blood fat, reducing blood pressure, nourishing liver, protecting stomach and enhancing immune system, the spirulina industry in China enters a high-speed development period from 2005 to 2010, the yield is developed from more than 5000 tons to 2 ten thousand tons, when high-speed development is pursued, part of manufacturers reduce cost and the requirement on quality is reduced, and because the spirulina mainly grows in various fresh water and seawater and is easily polluted by the water environment, polycyclic aromatic hydrocarbons in the water are easily enriched after being absorbed by the spirulina, so that the spirulina threatens the human body. The adsorbent which has strong adsorption capacity and is easy to separate is required for adsorbing the polycyclic aromatic hydrocarbon in the spirulina; the method for adsorbing polycyclic aromatic hydrocarbon reported at present is mostly used for adsorbing polycyclic aromatic hydrocarbon in soil and atmosphere, but the method for adsorbing polycyclic aromatic hydrocarbon in spirulina is not reported yet.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a method for removing polycyclic aromatic hydrocarbon by enrichment, and solves the problem that the polycyclic aromatic hydrocarbon threatens human bodies.
In order to solve the technical problems, the invention adopts the technical scheme that: the method for enriching and removing the polycyclic aromatic hydrocarbon comprises the following steps:
step 1: synthesizing a polycyclic aromatic hydrocarbon adsorbent;
the method for synthesizing the polycyclic aromatic hydrocarbon adsorbent comprises the following steps: synthesis of Fe by hydrothermal method3O4Magnetic microspheres, then adding Fe into buffer solution with pH of 8.0-9.03O4Stirring the magnetic microspheres and dopamine hydrochloride for 20-28h to obtain dopamine-coated Fe3O4Magnetic microsphere, vacuum drying at 35-45 deg.C for 10-14h, and coating dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in methanol solution containing 10mM triethylamine, adding bis-sulfhydryl compound, stirring at 25 deg.C for 16-20h for modification, and coating modified dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in acetonitrile, adding 1-vinyl-3-octadecyl imidazole bromide, adding azodiacetonitrile, reacting for 16-20h at 65-75 ℃ under the protection of nitrogen by mechanical stirring, washing with ethanol for 2-5 times, and vacuum drying at 55-65 ℃ overnight to obtain the polycyclic aromatic hydrocarbon adsorbent;
the hydrothermal method is utilized to synthesize Fe3O4The method of magnetic microspheres is as follows:
weighing 0.675g FeCl3·6H2Dissolving O in 20mL of ethylene glycol, magnetically stirring, and adding 1.8g of NaAc 3H after complete dissolution2O, 0.5g of polyethylene glycol, continuously stirring for 30min, transferring into a 50ml reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 10h, cooling to room temperature, separating precipitates by an additional magnet, washing the obtained magnetic microspheres to be neutral by a large amount of deionized water and absolute ethyl alcohol respectively, and vacuum drying at 40 ℃ for 12 h;
step 2: polycyclic aromatic hydrocarbon is enriched by the polycyclic aromatic hydrocarbon adsorbent;
the method for enriching polycyclic aromatic hydrocarbon by the polycyclic aromatic hydrocarbon adsorbent comprises the following steps:
weighing 30mg of polycyclic aromatic hydrocarbon adsorbent in a beaker, activating with acetonitrile for 2 times, then activating with water for 2 times, adding 50mL of a sample to be removed of polycyclic aromatic hydrocarbon, and carrying out ultrasonic treatment for 10min to ensure that the polycyclic aromatic hydrocarbon adsorbent fully enriches polycyclic alkane; and placing the magnet at the bottom of the beaker to make the polycyclic aromatic hydrocarbon adsorbent adsorbed on the magnet, wherein the supernatant is the sample from which the polycyclic aromatic hydrocarbon is removed.
The invention has the beneficial effects that: the polycyclic aromatic hydrocarbon adsorbent is synthesized by a sulfydryl-alkene click chemistry method, wherein sulfydryl-alkene click chemistry is one of click chemistry modules, so that the click chemistry adsorbent has the advantages of rich click chemistry reaction raw materials, mild reaction conditions, good product stereoselectivity, high yield, simple reaction post-treatment and product separation, and reaction byproducts are environment-friendly; the reaction does not need a metal catalyst, can generate free radicals through photoinitiation and thermal initiation, and is simple and efficient; at present, reports of modifying imidazole ionic liquid on the surface of magnetic nanoparticles by a mercapto-alkene click chemistry method are few, and particularly, reports of modifying imidazole ionic liquid for preparing polycyclic aromatic hydrocarbon adsorbents are not found. The prepared polycyclic aromatic hydrocarbon adsorbent is used for adsorbing polycyclic aromatic hydrocarbon, the adsorption efficiency is high, and the adsorbent can be separated only by a magnet due to the magnetism of the prepared polycyclic aromatic hydrocarbon adsorbent; the enrichment and elution conditions of 15 polycyclic aromatic hydrocarbons were optimized, the methodological parameters were examined, and the data show: the method has good linear relation and precision; the method is used for detecting the polycyclic aromatic hydrocarbon in the spirulina, and the quantitative limit of the method is 0.031-0.49 mug/L; except for the low recovery rate of Naphthalene (NAP) (52.9% -66.7%), the recovery rate of other 14 polycyclic aromatic hydrocarbons is 78.4% -107.1%.
Drawings
FIG. 1 is Fe3O4、Fe3O4@ DA and Fe3O4XRD pattern of @ DA-IL;
FIG. 2 is Fe3O4@ DA and Fe3O4FT-IR plot for @ DA-IL;
FIG. 3 is Fe3O4And Fe3O4SEM picture of @ DA-IL;
FIG. 4 is Fe3O4And Fe3O4TEM image of @ DA-IL;
FIG. 5 shows different doses of Fe3O4The amount of adsorbed polycyclic aromatic hydrocarbons of @ DA-IL;
FIG. 6 is Fe3O4Recovery of @ DA-IL in polycyclic aromatic hydrocarbon solutions of different concentrations;
FIG. 7 is Fe3O4Influence of the time for which @ DA-IL adsorbs polycyclic aromatic hydrocarbons on the adsorption efficiency.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
The invention provides a method for removing polycyclic aromatic hydrocarbon in an enrichment way, which comprises the following steps:
step 1: synthesizing a polycyclic aromatic hydrocarbon adsorbent;
the synthesized polycyclic aromatic hydrocarbon adsorbent is prepared by synthesizing Fe by using a hydrothermal method3O4Magnetic microsphere with Fe coated with dopamine3O4Magnetic microspheres are modified by a dimercapto compound to prepare a polycyclic aromatic hydrocarbon adsorbent;
step 2: the polycyclic aromatic hydrocarbon adsorbent is rich in polycyclic aromatic hydrocarbon.
From the above description, the polycyclic aromatic hydrocarbon adsorbent is synthesized by a mercapto-alkene click chemistry method, and the mercapto-alkene click chemistry is one of click chemistry modules, so that the click chemistry adsorbent has the advantages of rich click chemistry reaction raw materials, mild reaction conditions, good product stereoselectivity, high yield, simple reaction post-treatment and product separation, and reaction byproducts are environment-friendly; the reaction does not need a metal catalyst, can generate free radicals through photoinitiation and thermal initiation, and is simple and efficient; at present, reports of modifying imidazole ionic liquid on the surface of magnetic nanoparticles by a mercapto-alkene click chemistry method are few, and particularly, reports of modifying imidazole ionic liquid for preparing polycyclic aromatic hydrocarbon adsorbents are not found. The prepared polycyclic aromatic hydrocarbon adsorbent is used for adsorbing polycyclic aromatic hydrocarbon, the adsorption efficiency is high, and the adsorbent can be separated only by a magnet due to the magnetism of the prepared polycyclic aromatic hydrocarbon adsorbent; the enrichment and elution conditions of 15 polycyclic aromatic hydrocarbons were optimized, the methodological parameters were examined, and the data show: the method has good linear relation and precision; the method is used for detecting the polycyclic aromatic hydrocarbon in the spirulina, and the quantitative limit of the method is 0.031-0.49 mug/L; except for the low recovery rate of Naphthalene (NAP) (52.9% -66.7%), the recovery rate of other 14 polycyclic aromatic hydrocarbons is 78.4% -107.1%.
Further, the method for synthesizing the polycyclic aromatic hydrocarbon adsorbent in the step 1 comprises the following steps:
synthesis of Fe by hydrothermal method3O4Magnetic microspheres, then adding Fe into buffer solution with pH of 8.0-9.03O4Stirring the magnetic microspheres and dopamine hydrochloride for 20-28h to obtain dopamine-coated Fe3O4Magnetic microsphere, vacuum drying at 35-45 deg.C for 10-14h, and coating dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in methanol solution containing 10mM triethylamine, adding bis-sulfhydryl compound, stirring at 25 deg.C for 16-20h for modification, and coating modified dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in acetonitrile, adding 1-vinyl-3-octadecyl imidazole bromide, adding azodiacetonitrile, and mechanically stirring for reacting for 16-20h at 65-75 ℃ under the protection of nitrogen to obtain dopamine-coated Fe3O4And washing the magnetic microspheres with ethanol for 2-5 times, and vacuum-drying at 55-65 ℃ overnight to obtain the polycyclic aromatic hydrocarbon adsorbent.
As can be seen from the above description, the dopamine is used to coat Fe3O4The magnetic microsphere is modified by a dimercapto compound, and the obtained product has strong adsorption capacity on polycyclic aromatic hydrocarbon in the spirulina.
Further, a preferred method for synthesizing the polycyclic aromatic hydrocarbon adsorbent in the step 1 is as follows:
synthesis of Fe by hydrothermal method3O4Magnetic microspheres, then adding Fe to a buffer solution of pH8.53O4Stirring the magnetic microspheres and dopamine hydrochloride for 24 hours to prepare dopamine-coated Fe3O4Magnetic microsphere, vacuum drying at 40 deg.C for 12 hr, and coating dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in methanol solution containing 10mM triethylamine, adding a dimercapto compound, stirring at 25 ℃ for 18h for modification, and coating modified dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in acetonitrile, adding 1-vinyl-3-octadecyl imidazole bromine salt, adding azodiacetonitrile, mechanically stirring and reacting for 18h at 70 ℃ under the protection of nitrogen, washing for 3 times by using ethanol, and performing vacuum drying at 60 ℃ overnight to obtain the polycyclic aromatic hydrocarbon adsorbent.
From the above description, the synthesis conditions of the polycyclic aromatic hydrocarbon adsorbent are further optimized to obtain the high-quality polycyclic aromatic hydrocarbon adsorbent, so that the prepared adsorbent has higher adsorption efficiency on polycyclic aromatic hydrocarbon.
Further, the hydrothermal method is utilized to synthesize Fe3O4The method of magnetic microspheres is as follows:
weighing 0.675g FeCl3·6H2O was dissolved in 20mL of ethylene glycol. Magnetically stirring, adding 1.8g NaAc.3H after dissolving completely2O and 0.5g of polyethylene glycol, continuously stirring for 30min, transferring into a 50ml reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 10h, cooling to room temperature, and separating precipitates by an additional magnet. The obtained magnetic microspheres are respectively washed to be neutral by a large amount of deionized water and absolute ethyl alcohol, and are dried for 12 hours in vacuum at the temperature of 40 ℃.
As can be seen from the above description, the hydrothermal synthesis of Fe is preferred3O4Conditions of the magnetic microsphere method to obtain high quality Fe3O4The magnetic microspheres are beneficial to the synthesis of high-quality polycyclic aromatic hydrocarbon adsorbents.
Further, the method for enriching and removing the polycyclic aromatic hydrocarbon is used for removing the polycyclic aromatic hydrocarbon in the spirulina.
The method for removing polycyclic aromatic hydrocarbon by enrichment is used for removing polycyclic aromatic hydrocarbon in spirulina and also comprises the steps of preparing spirulina extracting solution; the method for preparing the spirulina extracting solution comprises the following steps:
weighing 5.0g of spirulina, adding 25mL of acetonitrile, ultrasonically mixing uniformly, shaking on a shaking table overnight, filtering, and uniformly mixing the filtrate obtained by filtering with water according to a ratio of 1:2 to prepare a water-acetonitrile mixed phase spirulina extract for later use.
The prepared polycyclic aromatic hydrocarbon adsorbent is used for adsorbing polycyclic aromatic hydrocarbon in the spirulina, the adsorption efficiency is high, and the adsorbent can be separated from the spirulina extracting solution only by a magnet due to the magnetism of the prepared polycyclic aromatic hydrocarbon adsorbent; the enrichment and elution conditions of 15 polycyclic aromatic hydrocarbons were optimized, the methodological parameters were examined, and the data show: the method has good linear relation and precision; the method is used for detecting the polycyclic aromatic hydrocarbon in the spirulina, and the quantitative limit of the method is 0.031-0.49 mug/L; except for the low recovery rate of Naphthalene (NAP) (52.9% -66.7%), the recovery rate of other 14 polycyclic aromatic hydrocarbons is 78.4% -107.1%.
The sample is prepared into a water phase liquid form, which is beneficial to the polycyclic aromatic hydrocarbon adsorbent to adsorb polycyclic aromatic hydrocarbon in the water phase.
Further, the method for enriching and removing the polycyclic aromatic hydrocarbon is used for removing the polycyclic aromatic hydrocarbon in the environmental water.
The polycyclic aromatic hydrocarbon adsorbent can effectively adsorb polycyclic aromatic hydrocarbon in environmental water and prevent the polycyclic aromatic hydrocarbon in the water from influencing human health.
Further, the polycyclic aromatic hydrocarbon adsorbent in the step 2 is enriched in polycyclic aromatic hydrocarbons by the following method:
weighing 30mg of polycyclic aromatic hydrocarbon adsorbent in a beaker, activating with acetonitrile for 2 times, then activating with water for 2 times, adding 50mL of a sample to be removed of polycyclic aromatic hydrocarbon, and carrying out ultrasonic treatment for 10min to ensure that the polycyclic aromatic hydrocarbon adsorbent fully enriches polycyclic alkane; and placing the magnet at the bottom of the beaker to make the polycyclic aromatic hydrocarbon adsorbent adsorbed on the magnet, wherein the supernatant is the sample from which the polycyclic aromatic hydrocarbon is removed.
From the above description, the preferable method for adsorbing polycyclic aromatic hydrocarbons in a sample by using the polycyclic aromatic hydrocarbon adsorbent requires only 10min of ultrasound to complete adsorption, and only a magnet is needed to separate the polycyclic aromatic hydrocarbon adsorbent.
Example 1
1. A method for removing polycyclic aromatic hydrocarbon in spirulina comprises the following steps:
step 1: synthesizing a polycyclic aromatic hydrocarbon adsorbent;
synthesis of Fe by hydrothermal method3O4Magnetic microspheres, 0.675g FeCl was weighed3·6H2O was dissolved in 20mL of ethylene glycol. Magnetically stirring, adding 1.8g NaAc.3H after dissolving completely2O and 0.5g of polyethylene glycol, continuously stirring for 30min, transferring into a 50ml reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 10h, cooling to room temperature, and separating precipitates by an additional magnet. The obtained magnetic microspheres are respectively washed to be neutral by a large amount of deionized water and absolute ethyl alcohol, and are dried for 12 hours in vacuum at the temperature of 40 ℃.
Then adding dopamine into buffer solution with pH of 8.5, mechanically stirring for 24h to obtain dopamine-coated particles, and vacuum drying at 40 deg.CAfter 12h, ultrasonically dispersing the particles in a methanol solution of 10mM triethylamine, adding a dimercapto compound, mechanically stirring for 18h at normal temperature for modification, ultrasonically dispersing the modified particles in acetonitrile, adding 1-vinyl-3-octadecyl imidazole bromide, adding azodiacetonitrile, and carrying out ultrasonic modification at 70 ℃ under N2Under the protection, mechanically stirring to react for 18h, washing with ethanol for 3 times, and vacuum drying at 60 ℃ overnight to obtain polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL。
Preparing spirulina extract;
weighing 5.0g of spirulina, adding 25mL of acetonitrile, ultrasonically mixing uniformly, shaking on a shaking table overnight, filtering, and uniformly mixing the filtrate obtained by filtering with water according to a ratio of 1:2 to prepare a water-acetonitrile mixed phase spirulina extract for later use.
Step 2: the polycyclic aromatic hydrocarbon adsorbent enriches the polycyclic aromatic hydrocarbon in the spirulina extracting solution;
weighing 30mg of polycyclic aromatic hydrocarbon adsorbent Fe3O4@ DA-IL in beaker, activating with acetonitrile for 2 times, activating with water for 2 times, adding 50mL Spirulina extractive solution, and subjecting to ultrasonic treatment for 10min to allow polycyclic aromatic hydrocarbon adsorbent Fe3O4@ DA-IL is used for fully enriching the polycyclic alkane in the spirulina extracting solution; placing magnet at the bottom of beaker to make Fe3O4The @ DA-IL is adsorbed on the magnet, and the supernatant is the spirulina extract without polycyclic aromatic hydrocarbons.
2. A method for removing polycyclic aromatic hydrocarbons from environmental water, comprising the steps of:
step 1: synthesizing a polycyclic aromatic hydrocarbon adsorbent;
synthesis of Fe by hydrothermal method3O4Magnetic microspheres, 0.675g FeCl was weighed3·6H2O was dissolved in 20mL of ethylene glycol. Magnetically stirring, adding 1.8g NaAc.3H after dissolving completely2O and 0.5g of polyethylene glycol, continuously stirring for 30min, transferring into a 50ml reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 10h, cooling to room temperature, and separating precipitates by an additional magnet. The obtained magnetic microspheres are respectively washed to be neutral by a large amount of deionized water and absolute ethyl alcohol, and are dried for 12 hours in vacuum at the temperature of 40 ℃.
Then is atAdding dopamine into buffer solution with pH of 8.5, mechanically stirring for 24h to obtain dopamine-coated particles, drying at 40 ℃ in vacuum for 12h, ultrasonically dispersing the dopamine-coated particles in 10mM triethylamine methanol solution, adding a dimercapto compound, mechanically stirring for 18h at normal temperature for modification, ultrasonically dispersing the modified particles in acetonitrile, adding 1-vinyl-3-octadecyl imidazole bromine salt, adding azodiacetonitrile butadiene, and performing N-phase reaction at 70 ℃ to obtain the dopamine-coated particles2Under the protection, mechanically stirring to react for 18h, washing with ethanol for 3 times, and vacuum drying at 60 ℃ overnight to obtain polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL。
Refrigerating the environmental water by using a brown reagent bottle, standing before measurement, discarding the precipitate, filtering by using a 0.45 mu m filter membrane, and taking 50mL to be measured.
Step 2: the polycyclic aromatic hydrocarbon adsorbent enriches the polycyclic aromatic hydrocarbon in the environmental water;
weighing 30mg of polycyclic aromatic hydrocarbon adsorbent Fe3O4@ DA-IL in a beaker, activating with acetonitrile for 2 times, activating with water for 2 times, adding 50mL of ambient water, and subjecting to ultrasonic treatment for 10min to allow the polycyclic aromatic hydrocarbon adsorbent Fe3O4@ DA-IL enriches sufficiently the polycyclic alkanes in the environmental water; placing magnet at the bottom of beaker to make Fe3O4The @ DA-IL is adsorbed on the magnet, and the supernatant is the environmental water from which the polycyclic aromatic hydrocarbons are removed.
2. Material characterization of the polycyclic aromatic hydrocarbon adsorbent:
as shown in FIG. 1, the prepared Fe was subjected to X-ray powder diffractometry3O4，Fe3O4@ DA and Fe3O4@ DA-IL. As can be seen from FIG. 1, Fe was produced3O4And Fe3O4Fe appears in XRD diffraction peaks of @ DA-IL3O46 characteristic peaks of (1) respectively corresponding to Fe3O4Characteristic crystal planes of (220), (331), (400), (422), (511) and (440) of (A), indicating Fe3O4The preparation is successful and the magnetic core is not changed in the post-modification process.
FIG. 2 is Fe3O4@ DA and Fe3O4Infrared spectrogram of @ DA-IL magnetic microsphere. In the figure, 1280cm-1 is the alkyl group C-NAbsorption Peak of extension vibration, 1429cm-1Is CH3Is 1621cm-1Tensile vibration absorption peak at C ═ C and C ═ N, 2923cm-1Is CH2Shows that the 1-vinyl-3-octadecyl imidazole bromide salt is combined with Fe3O4@ DA surface.
FIG. 3 is Fe3O4And Fe3O4SEM image of @ DA-IL magnetic microspheres. As can be seen from FIG. 3, Fe3O4Is spherical particles and is uniformly dispersed. Coating [ VC)18Im]After Br, the particle size is increased, a light-color irregular shell is formed on the surface of the nano particle, and the particle dispersibility is good.
FIG. 4 is a TEM image, and Fe can be seen3O4Spherical, uniform and good in dispersibility, and coated Fe3O4The @ DA-IL sphere is unchanged, and the shell thickness is relatively uniform at about 50 nm.
Unmodified Fe3O4The saturation magnetization reaches 84emu/g, is reduced to 46emu/g after being wrapped by dopamine, and slightly increases to 53emu/g after being wrapped by a dodecyl long chain, because when the dopamine is wrapped, a part of dopamine is polymerized into nonmagnetic particles by self, the average magnetization of a wrapping material is reduced, and the nonmagnetic dopamine polymer is removed during final modification. The magnetization of the synthetic material still belongs to a high saturation magnetization, which will facilitate a fast magnetic separation after enrichment.
3. The condition of adsorbing the polycyclic aromatic hydrocarbon by the polycyclic aromatic hydrocarbon adsorbent is optimized:
as polycyclic aromatic hydrocarbons are a series of compounds with similar structures and properties, in order to simplify the data analysis steps, PHE, ANT, FLT and PYR standard mixed solutions with higher sensitivity are selected as analysis objects to optimize the magnetic solid phase extraction conditions, and the influence of the dosage of an adsorbent, the extraction time, the type of an eluent and the elution time on the extraction effect is examined by using 50mL10 mu g/L standard mixed solution.
10mg, 20mg, 30mg, 50mg and 100mg of Fe were weighed out separately3O4@ DA-IL 50mL10 μg/L of the four polycyclic aromatic hydrocarbon mixed standard solutions are soaked overnight, then the supernatant is discarded under an external magnetic field, the mixed standard solutions are washed by water, and then the target substances on the magnetic nanoparticles are eluted by acetonitrile for determination, and the result is shown in figure 5. It can be seen from the figure that, the elution amount gradually increases with the increase of the dosage of the adsorbent, and when the dosage of the adsorbent is above 30mg, the elution amount of the polycyclic aromatic hydrocarbon is basically stable, the dosage of the adsorbent continues to increase, and the elution amount does not change obviously.
30mg of magnetic microspheres are weighed, and are soaked in 50mL0.01, 0.02, 0.2, 1, 10, 50 and 100 mu g/L polycyclic aromatic hydrocarbon mixed standard solution respectively for overnight and then treated by the same method, and the result is shown in figure 6, and it can be seen from the figure that the enrichment recovery rate of the magnetic nanoparticle material is 60-80% when the concentration of the target is lower than 0.2 mu g/L, because the contact probability of the adsorption material and the target is lower when the concentration is low, and longer balance time is needed, but the enrichment efficiency can still reach more than 60%, which indicates that the specificity of the enrichment material to the polycyclic aromatic hydrocarbon is good, because: nanostructured Fe3O4The peripheral surface area of the @ DA-IL is very large, the surface of the @ DA-IL contains rich benzene ring groups, the long alkane chain enables intermolecular force between the hydrophobic group of the material and the polycyclic aromatic hydrocarbon to be enhanced, and the benzene ring and the imidazole structure on the chain easily form a n-l conjugated electron cloud with the benzene ring of the polycyclic aromatic hydrocarbon so as to be adsorbed to Fe3O4@ DA-IL surface; the enrichment efficiency is best when the concentration of the polycyclic aromatic hydrocarbon is 0.2-10 mu g/L, the recovery rate is 75-108%, and when the concentration of the target substance exceeds 50 mu g/L, the recovery rate of the target substance begins to decline, which indicates that the adsorption amount reaches saturation.
Fe3O4The adsorption efficiency is directly influenced by the time for adsorbing polycyclic aromatic hydrocarbon of @ DA-IL, and the adsorption efficiency is reduced due to the fact that the adsorbents are mutually adsorbed, agglomerated and settled due to the magnetism of the adsorbents, so that the adsorption materials are required to be dispersed in the solution in an ultrasonic mode so that the materials can be fully suspended in the sample solution for adsorption, and the influence of different adsorption times (5min, 10min, 15min, 20min and 25min) on the adsorption effect is examined as shown in FIG. 7. As can be seen from the graph, the adsorption amount increases with the increase of the adsorption time, and when the adsorption time is 10min, the adsorption reaches a steady stateThe adsorption time is prolonged, and the adsorption quantity is basically unchanged.
In conclusion, the beneficial effects of the invention are as follows: the polycyclic aromatic hydrocarbon adsorbent is synthesized by a sulfydryl-alkene click chemistry method, wherein sulfydryl-alkene click chemistry is one of click chemistry modules, so that the click chemistry adsorbent has the advantages of rich click chemistry reaction raw materials, mild reaction conditions, good product stereoselectivity, high yield, simple reaction post-treatment and product separation, and reaction byproducts are environment-friendly; the reaction does not need a metal catalyst, can generate free radicals through photoinitiation and thermal initiation, and is simple and efficient; at present, reports of modifying imidazole ionic liquid on the surface of magnetic nanoparticles by a mercapto-alkene click chemistry method are few, and particularly, reports of modifying imidazole ionic liquid for preparing polycyclic aromatic hydrocarbon adsorbents are not found. The prepared polycyclic aromatic hydrocarbon adsorbent is used for adsorbing polycyclic aromatic hydrocarbon in the spirulina, the adsorption efficiency is high, and the adsorbent can be separated from the spirulina extracting solution only by a magnet due to the magnetism of the prepared polycyclic aromatic hydrocarbon adsorbent; the enrichment and elution conditions of 15 polycyclic aromatic hydrocarbons were optimized, the methodological parameters were examined, and the data show: the method has good linear relation and precision; the method is used for detecting the polycyclic aromatic hydrocarbon in the spirulina, and the quantitative limit of the method is 0.031-0.49 mug/L; the recovery of 14 polycyclic aromatic hydrocarbons, except Naphthalene (NAP), was 78.4% -107.1%.
Coating Fe with dopamine3O4The magnetic microsphere is modified by a dimercapto compound, and the obtained product has strong adsorption capacity on polycyclic aromatic hydrocarbon in the spirulina.
Further optimizing the synthesis conditions of the polycyclic aromatic hydrocarbon adsorbent to obtain the high-quality polycyclic aromatic hydrocarbon adsorbent, so that the prepared adsorbent has higher adsorption efficiency on polycyclic aromatic hydrocarbon in the spirulina.
Preferred hydrothermal method for synthesizing Fe3O4Conditions of the magnetic microsphere method to obtain high quality Fe3O4The magnetic microspheres are beneficial to the synthesis of high-quality polycyclic aromatic hydrocarbon adsorbents.
Further optimizing hydrothermal method for synthesizing Fe3O4Conditions of the magnetic microsphere method to obtain higher quality Fe3O4The magnetic microspheres are more beneficial to the synthesis of high-quality polycyclic aromatic hydrocarbon adsorbents.
The spirulina is prepared into a liquid form, and the polycyclic aromatic hydrocarbon adsorbent is favorable for adsorbing polycyclic aromatic hydrocarbon in the spirulina.
Preferably, the method for adsorbing the spirulina extract by the polycyclic aromatic hydrocarbon adsorbent can complete adsorption only by ultrasonic treatment for 10min, and the polycyclic aromatic hydrocarbon adsorbent can be separated only by a magnet.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (4)
1. A method for removing polycyclic aromatic hydrocarbon in an enrichment way is characterized in that: the method comprises the following steps:
step 1: synthesizing a polycyclic aromatic hydrocarbon adsorbent;
the method for synthesizing the polycyclic aromatic hydrocarbon adsorbent comprises the following steps: synthesis of Fe by hydrothermal method3O4Magnetic microspheres, then adding Fe into buffer solution with pH of 8.0-9.03O4Stirring the magnetic microspheres and dopamine hydrochloride for 20-28h to obtain dopamine-coated Fe3O4Magnetic microsphere, vacuum drying at 35-45 deg.C for 10-14h, and coating dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in methanol solution containing 10mM triethylamine, adding bis-sulfhydryl compound, stirring at 25 deg.C for 16-20h for modification, and coating modified dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in acetonitrile, adding 1-vinyl-3-octadecyl imidazole bromide, adding azodiacetonitrile, mechanically stirring for reacting for 16-20h at 65-75 ℃ under the protection of nitrogen, washing with ethanol, and vacuum drying to obtain the polycyclic aromatic hydrocarbon adsorbent;
the hydrothermal method is utilized to synthesize Fe3O4The method of magnetic microspheres is as follows:
weighing 0.675g FeCl3·6H2Dissolving O in 20mL of ethylene glycol, magnetically stirring, and adding1.8gNaAc·3H2O, 0.5g of polyethylene glycol, continuously stirring for 30min, transferring into a 50ml reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 10h, cooling to room temperature, separating precipitates by an additional magnet, washing the obtained magnetic microspheres to be neutral by a large amount of deionized water and absolute ethyl alcohol respectively, and vacuum drying at 40 ℃ for 12 h;
step 2: polycyclic aromatic hydrocarbon is enriched by the polycyclic aromatic hydrocarbon adsorbent;
the method for enriching polycyclic aromatic hydrocarbon by the polycyclic aromatic hydrocarbon adsorbent comprises the following steps:
weighing 30mg of polycyclic aromatic hydrocarbon adsorbent in a beaker, activating with acetonitrile for 2 times, then activating with water for 2 times, adding 50mL of a sample to be removed of polycyclic aromatic hydrocarbon, and carrying out ultrasonic treatment for 10min to ensure that the polycyclic aromatic hydrocarbon adsorbent fully enriches polycyclic alkane; and placing the magnet at the bottom of the beaker to make the polycyclic aromatic hydrocarbon adsorbent adsorbed on the magnet, wherein the supernatant is the sample from which the polycyclic aromatic hydrocarbon is removed.
2. The process for the enriched removal of polycyclic aromatic hydrocarbons according to claim 1, wherein: the method for synthesizing the polycyclic aromatic hydrocarbon adsorbent in the step 1 comprises the following steps:
synthesis of Fe by hydrothermal method3O4Magnetic microspheres, then adding Fe to a buffer solution of pH8.53O4Stirring the magnetic microspheres and dopamine hydrochloride for 24 hours to prepare dopamine-coated Fe3O4Magnetic microsphere, vacuum drying at 40 deg.C for 12 hr, and coating dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in methanol solution containing 10mM triethylamine, adding a dimercapto compound, stirring at 25 ℃ for 18h for modification, and coating modified dopamine with Fe3O4Ultrasonically dispersing magnetic microspheres in acetonitrile, adding 1-vinyl-3-octadecyl imidazole bromide, adding azodiacetonitrile, mechanically stirring and reacting for 18h at 70 ℃ under the protection of nitrogen, washing for 3 times by using ethanol, and performing vacuum drying at 60 ℃ overnight to obtain a polycyclic aromatic hydrocarbon adsorbent;
the hydrothermal method is utilized to synthesize Fe3O4The method of magnetic microspheres is as follows:
weighing 0.675g FeCl3·6H2Dissolving O in 20mL of ethylene glycol, magnetically stirring, and adding 1.8g of NaAc 3H after complete dissolution2And O and 0.5g of polyethylene glycol, continuously stirring for 30min, transferring into a 50ml reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 10h, cooling to room temperature, separating precipitates by an additional magnet, washing the obtained magnetic microspheres to be neutral by using a large amount of deionized water and absolute ethyl alcohol respectively, and vacuum-drying at 40 ℃ for 12 h.
3. The process for the enriched removal of polycyclic aromatic hydrocarbons according to claim 1, wherein: the method for removing polycyclic aromatic hydrocarbon by enrichment is used for removing polycyclic aromatic hydrocarbon in spirulina.
4. The process for the enriched removal of polycyclic aromatic hydrocarbons according to claim 1, wherein: the method for enriching and removing the polycyclic aromatic hydrocarbon is used for removing the polycyclic aromatic hydrocarbon in the environmental water.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011090428A1 (en) * | 2010-01-19 | 2011-07-28 | Organoclick Ab | Heterogeneous thiol-ene click modifications of solid polysaccharide-based materials |
| CN102145279A (en) * | 2010-02-05 | 2011-08-10 | 华中科技大学 | Method for preparing lysozyme molecular imprinting nano particles with magnetic responsiveness and extremely high adsorption capacity |
| CN102608093A (en) * | 2011-01-20 | 2012-07-25 | 中国科学院生态环境研究中心 | Detection method of polycyclic aromatic hydrocarbons (PAHs) |
| CN103183832A (en) * | 2011-12-28 | 2013-07-03 | 中国科学院青岛生物能源与过程研究所 | Preparation method for magnetic cellulose-chitosan composite microsphere |
| CN104689807A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | Am imidazole dicationic ionic liquid hydrophilic interaction chromatography stationary phase, and preparation and applications thereof |
| CN104892869A (en) * | 2015-06-23 | 2015-09-09 | 嘉兴学院 | Magnetic polymerization ionic liquid for detecting microcystic toxins and preparation method and application of magnetic polymerization ionic liquid |
| CN104910339A (en) * | 2015-06-23 | 2015-09-16 | 嘉兴学院 | Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4424586B2 (en) * | 2003-03-20 | 2010-03-03 | 株式会社ジャパンエナジー | Method for desulfurization of liquid hydrocarbons containing organic sulfur compounds |
| CN103706328B (en) * | 2014-01-17 | 2015-09-23 | 湖南大学 | The order mesoporous carbon adsorbent of aza magnetic, preparation method and application |
| CN104492494B (en) * | 2014-11-26 | 2017-05-03 | 绍兴文理学院 | Magnetic iron oxide-immobilized ionic liquid solid acid material catalyst and preparation method thereof |
| CN104971687A (en) * | 2015-07-20 | 2015-10-14 | 北京宝鸿锐科环境科技有限公司 | Efficient compound iron-based phosphorous-removing adsorbent as well as preparation method, application method and regeneration method thereof |
-
2016
- 2016-08-01 CN CN201810927445.2A patent/CN108940215B/en not_active Expired - Fee Related
- 2016-08-01 CN CN201810927478.7A patent/CN108940216B/en not_active Expired - Fee Related
- 2016-08-01 CN CN201810927213.7A patent/CN108927114B/en not_active Expired - Fee Related
- 2016-08-01 CN CN201610621741.0A patent/CN106111070B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011090428A1 (en) * | 2010-01-19 | 2011-07-28 | Organoclick Ab | Heterogeneous thiol-ene click modifications of solid polysaccharide-based materials |
| CN102145279A (en) * | 2010-02-05 | 2011-08-10 | 华中科技大学 | Method for preparing lysozyme molecular imprinting nano particles with magnetic responsiveness and extremely high adsorption capacity |
| CN102608093A (en) * | 2011-01-20 | 2012-07-25 | 中国科学院生态环境研究中心 | Detection method of polycyclic aromatic hydrocarbons (PAHs) |
| CN103183832A (en) * | 2011-12-28 | 2013-07-03 | 中国科学院青岛生物能源与过程研究所 | Preparation method for magnetic cellulose-chitosan composite microsphere |
| CN104689807A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | Am imidazole dicationic ionic liquid hydrophilic interaction chromatography stationary phase, and preparation and applications thereof |
| CN104892869A (en) * | 2015-06-23 | 2015-09-09 | 嘉兴学院 | Magnetic polymerization ionic liquid for detecting microcystic toxins and preparation method and application of magnetic polymerization ionic liquid |
| CN104910339A (en) * | 2015-06-23 | 2015-09-16 | 嘉兴学院 | Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid |
Non-Patent Citations (3)
| Title |
|---|
| Fe3O4 (iron oxide)-supported nanocatalysts:;Rakesh K. Sharma et al;《Green Chem》;20160418;全文 * |
| Poly(ionic liquid) Latexes Prepared by Dispersion Polymerization of Ionic;Jiayin Yuan et al;《Macromolecules》;20111231;全文 * |
| 通过巯基和炔基官能团的点击化学反应制备高分子抗菌涂层;李义和等;《中国化学会第30届学术年会摘要集》;20160701;全文 * |
Also Published As
| Publication number | Publication date |
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| CN108940216A (en) | 2018-12-07 |
| CN108940216B (en) | 2020-12-08 |
| CN108940215A (en) | 2018-12-07 |
| CN108927114A (en) | 2018-12-04 |
| CN108927114B (en) | 2020-10-30 |
| CN106111070B (en) | 2018-09-11 |
| CN106111070A (en) | 2016-11-16 |
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