CN108940215A - A kind of method of enriched removal polycyclic aromatic hydrocarbon - Google Patents
A kind of method of enriched removal polycyclic aromatic hydrocarbon Download PDFInfo
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Abstract
The present invention relates to a kind of methods of enriched removal polycyclic aromatic hydrocarbon.The following steps are included: step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；The synthesis polycyclic aromatic hydrocarbon adsorbent is to synthesize Fe using hydro-thermal method3O4Magnetic microsphere wraps up Fe using dopamine3O4Magnetic microsphere, and modified with double sulfhydryl compounds, polycyclic aromatic hydrocarbon adsorbent is made；Step 2: polycyclic aromatic hydrocarbon adsorbent is enriched with polycyclic aromatic hydrocarbon.Polycyclic aromatic hydrocarbon adsorbent is synthesized by sulfydryl-alkene clicking chemistry method, is used for absorbing multiring aromatic hydrocarbon, adsorption efficiency is high, is easily isolated, it is only necessary to which magnet can separating adsorbent.
Description
This case is with the applying date for 2016-08-01, and application No. is 201610621741.0, entitled " a kind of removing is polycyclic
The divisional application that the patent of invention of the method for aromatic hydrocarbons " carries out for female case.
Technical field
The present invention relates to a kind of methods of enriched removal polycyclic aromatic hydrocarbon.
Background technique
Polycyclic aromatic hydrocarbon is a kind of containing two or more phenyl ring or heterocycle in linear, horn shape or tufted arrangement
Property or nonpolar organic compound, there are tobacco smoke, vehicle exhaust, petroleum chemicals and unburnt coals, wood
In the organic compounds such as material, oil.Human body can be entered by food chain and breathing, can be enriched in human body, to influence gene table
It reaches, and causes to induce cancer, mutagenesis, teratogenesis and other diseases, be classified as priority pollutants by countries in the world.
Spirulina has anti-aging, anti anoxia, antifatigue, anti-radiation, reducing blood lipid, blood pressure lowering, nourishing the liver shield stomach enhancing immune
The effect of system, the spirulina industry entry high-speed development period in the China Nian Shi from 2005 to 2010, yield are sent out from more than 5000 tons
Exhibition is to 20,000 tons, and while pursuing high speed development, part of the manufacturer is to reduce cost, and the requirement to quality reduces, due to spirulina
It is mainly grown in various fresh water, in seawater, the pollution by water body environment is easy, after the polycyclic aromatic hydrocarbon in water body is absorbed by spirulina
It is easy enrichment, to constitute a threat to human body.Polycyclic aromatic hydrocarbon in absorption spirulina needs adsorption capacity strong, the suction being easily isolated
Attached dose；The method for the absorbing multiring aromatic hydrocarbon reported at present is chiefly used in adsorbing soil, the polycyclic aromatic hydrocarbon in atmosphere, and is suitable for absorption
The method of polycyclic aromatic hydrocarbon has not been reported in spirulina.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of method of enriched removal polycyclic aromatic hydrocarbon, solve polycyclic
The problem of aromatic hydrocarbons constitutes a threat to human body.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows: a kind of enriched polycyclic virtue of removal is provided
The method of hydrocarbon, comprising the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
The synthesis polycyclic aromatic hydrocarbon adsorbent method is as follows: synthesizing Fe using hydro-thermal method3O4Then magnetic microsphere exists
Fe is added in the buffer of pH8.0-9.03O4Dopamine package is made after stirring 20-28h in magnetic microsphere and Dopamine hydrochloride
Fe3O4Magnetic microsphere, after 35-45 DEG C of vacuum drying 10-14h, Fe that dopamine is wrapped up3O4Magnetic microsphere ultrasonic disperse is in containing
In the methanol solution for having 10mM triethylamine, the double sulfhydryl compounds of addition stir 16-20h at 25 DEG C and are modified, will be by repairing
The Fe of the dopamine package of decorations3O41- vinyl -3- octadecyl imidazoles bromide is added in acetonitrile in magnetic microsphere ultrasonic disperse,
Azo diethyl butyronitrile is added, under 65-75 DEG C of condition and nitrogen protection, mechanic whirl-nett reaction 16-20h, then rinsed with ethyl alcohol
2-5 times, 55-65 DEG C is dried in vacuum overnight, and obtains polycyclic aromatic hydrocarbon adsorbent；
It is described to synthesize Fe using hydro-thermal method3O4The method of magnetic microsphere is as follows:
Weigh 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol, magnetic agitation, until completely dissolved, is added
1.8gNaAc·3H2O, 0.5g polyethylene glycol continue after stirring 30min, move into the reaction kettle that 50ml liner is polytetrafluoroethylene (PTFE)
In, it after 200 DEG C of reaction 10h, is cooled to room temperature, by additional magnet sediment separate out, obtained magnetic microsphere is used largely respectively
Deionized water and dehydrated alcohol are washed to neutrality, 40 DEG C of vacuum drying 12h；
Step 2: polycyclic aromatic hydrocarbon adsorbent is enriched with polycyclic aromatic hydrocarbon；
The method of the polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon is as follows:
30mg polycyclic aromatic hydrocarbon adsorbent is weighed in beaker, is activated 2 times with acetonitrile, then is activated 2 times with water, 50mL is added and waits for
The sample of polycyclic aromatic hydrocarbon is removed, ultrasonic 10min makes polycyclic aromatic hydrocarbon adsorbent sufficiently be enriched with polycyoalkane；Magnet is placed in beaker
Bottom is adsorbed in polycyclic aromatic hydrocarbon adsorbent on magnet, and supernatant is the sample for removing polycyclic aromatic hydrocarbon.
The beneficial effects of the present invention are: the present invention synthesizes polycyclic aromatic hydrocarbon adsorbent, mercapto by sulfydryl-alkene clicking chemistry method
Base-alkene clicking chemistry is one of click chemistry module, not only there are click chemistry reaction raw materials to enrich, reaction condition temperature
With product stereoselectivity is good, yield is high, post-reaction treatment and product separate simply, and byproduct of reaction is environmentally friendly；It should
Class reaction is not necessarily to metallic catalyst, can be generated free radicals by light-initiated and hot initiation, and reaction is simple, efficient；Currently, passing through
Report of the sulfydryl-alkene clicking chemistry method by glyoxaline ion liquid modification to magnetic nanometer surface is also fewer, especially uses
It is had not been reported in obtained polycyclic aromatic hydrocarbon adsorbent.Using polycyclic aromatic hydrocarbon adsorbent absorbing multiring aromatic hydrocarbon obtained, adsorption efficiency
Height, since polycyclic aromatic hydrocarbon adsorbent obtained has magnetism, it is only necessary to which magnet can separating adsorbent；To the richness of 15 kinds of polycyclic aromatic hydrocarbons
Collection and elution requirement optimize, and investigate its methodology parameter, data are shown:, this method linear relationship and precision are good；With
The detection of polycyclic aromatic hydrocarbon in spirulina, method are quantitatively limited to 0.031-0.49 μ g/L；In addition to the rate of recovery of naphthalene (NAP) is lower
(52.9%~66.7%) outside, the rate of recovery of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Detailed description of the invention
Fig. 1 is Fe3O4、Fe3O4@DA and Fe3O4The XRD diagram of@DA-IL；
Fig. 2 is Fe3O4@DA and Fe3O4The FT-IR of@DA-IL schemes；
Fig. 3 is Fe3O4And Fe3O4The SEM of@DA-IL schemes；
Fig. 4 is Fe3O4And Fe3O4The TEM of@DA-IL schemes；
Fig. 5 is the Fe of various dose3O4The polycyclic aromatic hydrocarbon adsorbance of@DA-IL；
Fig. 6 is Fe3O4The rate of recovery of the@DA-IL in the polycyclic aromatic hydrocarbon solution of various concentration；
Fig. 7 is Fe3O4Influence of the time of@DA-IL absorbing multiring aromatic hydrocarbon to adsorption efficiency.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, below in conjunction with embodiment and cooperate attached
Figure is explained.
The present invention provides a kind of method of enriched removal polycyclic aromatic hydrocarbon, comprising the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
The synthesis polycyclic aromatic hydrocarbon adsorbent is to synthesize Fe using hydro-thermal method3O4Magnetic microsphere is wrapped up using dopamine
Fe3O4Magnetic microsphere, and modified with double sulfhydryl compounds, polycyclic aromatic hydrocarbon adsorbent is made；
Step 2: polycyclic aromatic hydrocarbon adsorbent is enriched with polycyclic aromatic hydrocarbon.
As can be seen from the above description, the present invention synthesizes polycyclic aromatic hydrocarbon adsorbent, sulfydryl-alkene by sulfydryl-alkene clicking chemistry method
Click chemistry is one of click chemistry module, not only there are click chemistry reaction raw materials to enrich, reaction condition is mild, product
Stereoselectivity is good, yield is high, post-reaction treatment and product separation are simple, and byproduct of reaction is environmentally friendly；Such reaction
It without metallic catalyst, can be generated free radicals by light-initiated and hot initiation, reaction is simple, efficient；Currently, passing through sulfydryl-
Report of the alkene clicking chemistry method by glyoxaline ion liquid modification to magnetic nanometer surface is also fewer, especially for being made
Polycyclic aromatic hydrocarbon adsorbent has not been reported.Using polycyclic aromatic hydrocarbon adsorbent absorbing multiring aromatic hydrocarbon obtained, adsorption efficiency is high, due to
Polycyclic aromatic hydrocarbon adsorbent obtained has magnetism, it is only necessary to which magnet can separating adsorbent；It enrichment to 15 kinds of polycyclic aromatic hydrocarbons and washes
De- condition optimizes, and investigates its methodology parameter, and data are shown:, this method linear relationship and precision are good；For spiral
The detection of polycyclic aromatic hydrocarbon in algae, method are quantitatively limited to 0.031-0.49 μ g/L；In addition to the rate of recovery lower (52.9% of naphthalene (NAP)
~66.7%) outside, the rate of recovery of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Further, it is as follows that polycyclic aromatic hydrocarbon adsorbent method is synthesized in the step 1:
Fe is synthesized using hydro-thermal method3O4Then Fe is added in the buffer of pH8.0-9.0 in magnetic microsphere3O4Magnetic microsphere
And Dopamine hydrochloride, the Fe that dopamine wraps up is made after stirring 20-28h3O4Magnetic microsphere, 35-45 DEG C of vacuum drying 10-14h
Afterwards, Fe dopamine wrapped up3O4Double sulfydryls are added in the methanol solution containing 10mM triethylamine in magnetic microsphere ultrasonic disperse
Compound stirs 16-20h at 25 DEG C and is modified, by the Fe of the dopamine package by modification3O4Magnetic microsphere ultrasonic disperse
In acetonitrile, 1- vinyl -3- octadecyl imidazoles bromide is added, azo diethyl butyronitrile is added, in 65-75 DEG C of condition and nitrogen
Under gas shielded, mechanic whirl-nett reaction 16-20h, the Fe of gained dopamine package3O4Magnetic microsphere is rinsed 2-5 times with ethyl alcohol again, 55-
65 DEG C are dried in vacuum overnight, and obtain polycyclic aromatic hydrocarbon adsorbent.
Seen from the above description, Fe is wrapped up using dopamine3O4Magnetic microsphere, and modified with double sulfhydryl compounds, it obtains
To product have very strong adsorption capacity to polycyclic aromatic hydrocarbon in spirulina.
Further, the method that polycyclic aromatic hydrocarbon adsorbent is preferably synthesized in the step 1 is as follows:
Fe is synthesized using hydro-thermal method3O4Then Fe is added in the buffer of pH8.5 in magnetic microsphere3O4Magnetic microsphere and salt
The Fe of dopamine package is made in sour dopamine, stirring afterwards for 24 hours3O4After 40 DEG C of vacuum drying 12h, dopamine is wrapped up for magnetic microsphere
Fe3O4Magnetic microsphere ultrasonic disperse is added double sulfhydryl compounds and stirs at 25 DEG C in the methanol solution containing 10mM triethylamine
It mixes 18h to be modified, by the Fe of the dopamine package by modification3O41- ethylene is added in acetonitrile in magnetic microsphere ultrasonic disperse
Base -3- octadecyl imidazoles bromide, adds azo diethyl butyronitrile, under 70 DEG C of conditions and nitrogen protection, mechanic whirl-nett reaction
18h is rinsed 3 times with ethyl alcohol, and 60 DEG C are dried in vacuum overnight, and obtain polycyclic aromatic hydrocarbon adsorbent.
Seen from the above description, the synthesis condition for advanced optimizing polycyclic aromatic hydrocarbon adsorbent obtains the polycyclic virtue of high quality
Hydrocarbon adsorbent makes adsorbent obtained have higher adsorption efficiency for polycyclic aromatic hydrocarbon.
Further, described to synthesize Fe using hydro-thermal method3O4The method of magnetic microsphere is as follows:
Weigh 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol.Magnetic agitation adds until completely dissolved
1.8gNaAc·3H2O, 0.5g polyethylene glycol continue after stirring 30min, move into the reaction kettle that 50ml liner is polytetrafluoroethylene (PTFE)
In, after 200 DEG C of reaction 10h, it is cooled to room temperature, passes through additional magnet sediment separate out.Obtained magnetic microsphere is used largely respectively
Deionized water and dehydrated alcohol are washed to neutrality, 40 DEG C of vacuum drying 12h.
Seen from the above description, preferably hydro-thermal method synthesizes Fe3O4The condition of the method for magnetic microsphere, obtains high quality
Fe3O4Magnetic microsphere is conducive to the synthesis of high quality polycyclic aromatic hydrocarbon adsorbent.
Further, the method for the enriched removal polycyclic aromatic hydrocarbon is used to remove the polycyclic aromatic hydrocarbon in spirulina.
It further includes preparation spiral that the method for the enriched removal polycyclic aromatic hydrocarbon, which is used to remove the polycyclic aromatic hydrocarbon in spirulina,
Algae extracting solution；It is described that prepare spirulina extract method as follows:
5.0g spirulina is weighed, 25mL acetonitrile is added, ultrasound is shaken on shaking table overnight after mixing, and filtering will filter
To filtrate and water according to 1:2 mixing, that water-acetonitrile mixed phase spirulina extract is made is spare.
Using the polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon adsorbent obtained absorption spirulina, adsorption efficiency is high, due to obtained
Polycyclic aromatic hydrocarbon adsorbent have magnetism, it is only necessary to magnet can in spirulina extract separating adsorbent；To 15 kinds of polycyclic aromatic hydrocarbons
Enrichment and elution requirement optimize, investigate its methodology parameter, data are shown:, this method linear relationship and precision are good
It is good；For the detection of polycyclic aromatic hydrocarbon in spirulina, method is quantitatively limited to 0.031-0.49 μ g/L；In addition to the rate of recovery of naphthalene (NAP)
Lower (52.9%~66.7%) outside, the rate of recovery of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Aqueous phase liquid form is made in sample, is conducive to the polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon adsorbent absorption water phase.
Further, the method for the enriched removal polycyclic aromatic hydrocarbon is used to remove the polycyclic aromatic hydrocarbon in ambient water.
Water can be adsorbed effectively as the essential resource of human lives using polycyclic aromatic hydrocarbon adsorbent of the present invention
Polycyclic aromatic hydrocarbon in ambient water prevents the polycyclic aromatic hydrocarbon in water from influencing human health.
Further, the method for polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon is as follows in the step 2:
30mg polycyclic aromatic hydrocarbon adsorbent is weighed in beaker, is activated 2 times with acetonitrile, then is activated 2 times with water, 50mL is added and waits for
The sample of polycyclic aromatic hydrocarbon is removed, ultrasonic 10min makes polycyclic aromatic hydrocarbon adsorbent sufficiently be enriched with polycyoalkane；Magnet is placed in beaker
Bottom is adsorbed in polycyclic aromatic hydrocarbon adsorbent on magnet, and supernatant is the sample for removing polycyclic aromatic hydrocarbon.
Seen from the above description, preferably in polycyclic aromatic hydrocarbon adsorbent adsorption sample polycyclic aromatic hydrocarbon method, it is only necessary to ultrasound
Absorption can be completed in 10min, it is only necessary to the i.e. separable polycyclic aromatic hydrocarbon adsorbent of magnet.
Embodiment 1
1, a kind of method for removing polycyclic aromatic hydrocarbon in spirulina, comprising the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
Fe is synthesized using hydro-thermal method3O4Magnetic microsphere weighs 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol.Magnetic force
Stirring, until completely dissolved, adds 1.8gNaAc3H2O, 0.5g polyethylene glycol continue after stirring 30min, move into 50ml
Liner is after 200 DEG C of reaction 10h, to be cooled to room temperature in the reaction kettle of polytetrafluoroethylene (PTFE), pass through additional magnet sediment separate out.
Obtained magnetic microsphere is washed with a large amount of deionized waters and dehydrated alcohol to neutrality respectively, 40 DEG C of vacuum drying 12h.
Then it is added dopamine in the buffer of pH8.5, mechanical stirring is made dopamine afterwards for 24 hours and wraps up particle, and 40 DEG C
After being dried in vacuo 12h, by its ultrasonic disperse in the methanol solution of 10mM triethylamine, double sulfhydryl compounds are added in normal temperature condition
Lower mechanical stirring 18h is modified, and by the particle ultrasonic disperse by modification in acetonitrile, 1- vinyl -3- octadecane is added
Base imidazoles bromide adds azo diethyl butyronitrile, in 70 DEG C of conditions and N2Under protection, mechanic whirl-nett reaction 18h is rinsed with ethyl alcohol
3 times, 60 DEG C are dried in vacuum overnight, and obtain polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL。
Prepare spirulina extract；
5.0g spirulina is weighed, 25mL acetonitrile is added, ultrasound is shaken on shaking table overnight after mixing, and filtering will filter
To filtrate and water according to 1:2 mixing, that water-acetonitrile mixed phase spirulina extract is made is spare.
Step 2: polycyclic aromatic hydrocarbon adsorbent is enriched with the polycyclic aromatic hydrocarbon in spirulina extract；
Weigh 30mg polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL is activated 2 times in beaker with acetonitrile, then is activated 2 times with water,
50mL spirulina extract is added, ultrasonic 10min makes polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL is sufficiently enriched with spirulina extract
In polycyoalkane；Magnet is placed in beaker bottom, makes Fe3O4@DA-IL is adsorbed on magnet, and supernatant is to remove polycyclic virtue
The spirulina extract of hydrocarbon.
2, a kind of method for removing polycyclic aromatic hydrocarbon in ambient water, comprising the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
Fe is synthesized using hydro-thermal method3O4Magnetic microsphere weighs 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol.Magnetic force
Stirring, until completely dissolved, adds 1.8gNaAc3H2O, 0.5g polyethylene glycol continue after stirring 30min, move into 50ml
Liner is after 200 DEG C of reaction 10h, to be cooled to room temperature in the reaction kettle of polytetrafluoroethylene (PTFE), pass through additional magnet sediment separate out.
Obtained magnetic microsphere is washed with a large amount of deionized waters and dehydrated alcohol to neutrality respectively, 40 DEG C of vacuum drying 12h.
Then it is added dopamine in the buffer of pH8.5, mechanical stirring is made dopamine afterwards for 24 hours and wraps up particle, and 40 DEG C
After being dried in vacuo 12h, by its ultrasonic disperse in the methanol solution of 10mM triethylamine, double sulfhydryl compounds are added in normal temperature condition
Lower mechanical stirring 18h is modified, and by the particle ultrasonic disperse by modification in acetonitrile, 1- vinyl -3- octadecane is added
Base imidazoles bromide adds azo diethyl butyronitrile, in 70 DEG C of conditions and N2Under protection, mechanic whirl-nett reaction 18h is rinsed with ethyl alcohol
3 times, 60 DEG C are dried in vacuum overnight, and obtain polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL。
Ambient water is refrigerated with brown reagent bottle, is first stood before measurement, is discarded sediment, take after 0.45 μm of membrane filtration
50mL, it is to be measured.
Step 2: the polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon adsorbent enrichment environment water；
Weigh 30mg polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL is activated 2 times in beaker with acetonitrile, then is activated 2 times with water,
50mL ambient water is added, ultrasonic 10min makes polycyclic aromatic hydrocarbon adsorbent Fe3O4Polynaphthene in the abundant enrichment environment water of@DA-IL
Hydrocarbon；Magnet is placed in beaker bottom, makes Fe3O4@DA-IL is adsorbed on magnet, and supernatant is the environment for removing polycyclic aromatic hydrocarbon
Water.
2, the material characterization of above-mentioned polycyclic aromatic hydrocarbon adsorbent:
Such as Fig. 1, with X-ray powder diffraction instrument to prepared Fe3O4, Fe3O4@DA and Fe3O4@DA-IL is analyzed.
As shown in Figure 1, the Fe of preparation3O4And Fe3O4There is Fe in the XRD diffraction maximum of@DA-IL3O46 characteristic peaks, respectively correspond
Fe3O4(220), (331), (400), (422), (511) and (440) feature crystal face, show Fe3O4It is successfully prepared and is repaired after
There is no variations for magnetic core during decorations.
Fig. 2 is Fe3O4@DA and Fe3O4The infrared spectrogram of@DA-IL magnetic microsphere.1280cm-1 is alkyl C-N in figure
Stretching vibration absorption peak, 1429cm-1It is CH3Asymmetric stretching absorption peak, 1621cm-1Place is the stretching vibration of C=C and C=N
Absorption peak, 2923cm-1It is CH2Asymmetric stretching absorption peak, illustrate that 1- vinyl -3- octadecyl imidazoles bromide is incorporated in
Fe3O4The surface@DA.
Fig. 3 is Fe3O4And Fe3O4The SEM of@DA-IL magnetic microsphere schemes.From figure 3, it can be seen that Fe3O4For spheric granules,
It is uniformly dispersed.Coat [VC18Im] after Br, partial size is increased, and nanoparticle surface forms the irregular shell of light color, particle point
It is good to dissipate property.
Fig. 4 is TEM figure, it can be seen that Fe3O4For spheroidal, particle uniformly and good dispersion, the Fe after package3O4@DA-
IL spherical shape is constant, the relatively uniform about 50nm of shell thickness.
Unmodified Fe3O4Saturation magnetization is up to 84emu/g, and 46emu/g is down to after dopamine wraps up, cladding
After dodecyl long-chain, saturation magnetization slightly rises to 53emu/g, this is because a part is more in dopamine package
Bar amine autohemagglutination synthesizes non-magnetic particle, reduces the average magnetization of lapping, non-magnetic more in last modification
Bar amine polymer is removed.The intensity of magnetization of synthetic material still falls within high saturation magnetization, this is beneficial to be enriched with
Quick Magneto separate afterwards.
3, the condition optimizing of above-mentioned polycyclic aromatic hydrocarbon adsorbent absorbing multiring aromatic hydrocarbon:
Since polycyclic aromatic hydrocarbon is a series of similar compound of structures, property is close, therefore to simplify data analysis step,
Selecting wherein with higher sensitivity PHE, ANT, FLT and PYR standard mixed solution herein is analysis object progress magnetic solid phase extraction
The optimization of condition is investigated adsorbent amount, extraction time, eluant, eluent type with the standard mixed solution of 50mL10 μ g/L and is washed
De- influence of the time to effect of extracting.
The Fe of 10mg, 20mg, 30mg, 50mg, 100mg are weighed respectively3O4@DA-IL tetra- kinds of polycyclic aromatic hydrocarbons of 50mL10 μ g/L
Mixed mark solution soaked overnight, liquid is then discarded supernatant under external magnetic field, is first washed with water, then on acetonitrile elution magnetic nanometer
Object be measured, as a result as shown in Figure 5.It can be seen from the figure that elution amount is gradually with the increase of adsorbent amount
Increase, when adsorbent amount is in 30mg or more, polycyclic aromatic hydrocarbon elution amount basically reaches stabilization, and quantity of sorbent continues growing, and washes
De- amount is not apparent from variation.
The magnetic microsphere of 30mg is weighed, uses 50mL0.01, the polycyclic aromatic hydrocarbon of 0.02,0.2,1,10,50,100 μ g/L respectively
Mixed mark solution soaked overnight, then same treatment, is as a result shown in Fig. 6, it can be seen from the figure that magnetic nanometer material is in object
Enriching and recovering rate when concentration is lower than 0.2 μ g/L is in 60%-80%, this is because adsorbent material and object when concentration is low
Contact probability is lower, needs longer equilibration time, but bioaccumulation efficiency remains to reach 60% enrichment material described above to more
The specificity of cycloaromatics is good, this is because: the Fe of nanostructure3O4The peripheral surface product of@DA-IL is very big, and surface is containing abundant
Benzene radicals, long alkane chain enhances the intermolecular force between the hydrophobic grouping of material and polycyclic aromatic hydrocarbon, simultaneously
Phenyl ring and glyoxaline structure on chain are easily and the phenyl ring of polycyclic aromatic hydrocarbon forms Л-Л conjugated electrons cloud to be adsorbed in Fe3O4@
The surface DA-IL；Bioaccumulation efficiency when polycyclic aromatic hydrocarbon concentration is in 0.2-10 μ g/L is best, and the rate of recovery works as target in 75-108%
When object concentration is more than 50 μ g/L, the rate of recovery of adsorbed target object is begun to decline, and adsorbance has reached saturation at this time for prompt.
Fe3O4The time of@DA-IL absorbing multiring aromatic hydrocarbon directly affects adsorption efficiency, since the magnetism of adsorbent itself makes
Adsorbent adsorbs conglomeration mutually and settling causes adsorption efficiency to reduce, therefore ultrasonic disperse makes material in the solution by adsorbent material
Material can sufficiently be suspended in sample solution and be adsorbed, investigate different adsorption times (5min, 10min, 15min, 20min and
It is 25min) as shown in Figure 7 to the influence of adsorption effect.It can be seen from the figure that the increase adsorbance with adsorption time also increases
Greatly, when adsorption time is 10min, absorption reaches stable state, and adsorption time extends, and adsorbance is basically unchanged.
In conclusion the beneficial effects of the present invention are: the present invention synthesizes polycyclic aromatic hydrocarbon by sulfydryl-alkene clicking chemistry method
Adsorbent, sulfydryl-alkene clicking chemistry are one of click chemistry modules, not only have click chemistry reaction raw materials abundant, anti-
Answer that mild condition, product stereoselectivity is good, yield is high, post-reaction treatment and product separation are simple, and byproduct of reaction is to ring
Border is friendly；Such reaction is not necessarily to metallic catalyst, can be generated free radicals by light-initiated and hot initiation, and reaction is simple, efficient；
Currently, the report by sulfydryl-alkene clicking chemistry method by glyoxaline ion liquid modification to magnetic nanometer surface is also fewer,
Especially had not been reported for polycyclic aromatic hydrocarbon adsorbent to be made.Using in polycyclic aromatic hydrocarbon adsorbent obtained absorption spirulina
Polycyclic aromatic hydrocarbon, adsorption efficiency is high, since polycyclic aromatic hydrocarbon adsorbent obtained has magnetism, it is only necessary to which magnet can be extracted in spirulina
Separating adsorbent in liquid；The enrichment and elution requirement of 15 kinds of polycyclic aromatic hydrocarbons are optimized, its methodology parameter is investigated, data are aobvious
Show: this method linear relationship and precision are good；For the detection of polycyclic aromatic hydrocarbon in spirulina, method is quantitatively limited to 0.031-
0.49μg/L；Other than naphthalene (NAP), the rate of recovery of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Fe is wrapped up using dopamine3O4Magnetic microsphere, and modified with double sulfhydryl compounds, obtained product is to spiral
Polycyclic aromatic hydrocarbon has very strong adsorption capacity in algae.
The synthesis condition for advanced optimizing polycyclic aromatic hydrocarbon adsorbent obtains the polycyclic aromatic hydrocarbon adsorbent of high quality, makes to be made
Adsorbent for the polycyclic aromatic hydrocarbon in spirulina have higher adsorption efficiency.
It is preferred that hydro-thermal method synthesizes Fe3O4The condition of the method for magnetic microsphere obtains the Fe of high quality3O4Magnetic microsphere, favorably
In the synthesis of high quality polycyclic aromatic hydrocarbon adsorbent.
Advanced optimize hydro-thermal method synthesis Fe3O4The condition of the method for magnetic microsphere obtains higher-quality Fe3O4It is magnetic
Microballoon is more advantageous to the synthesis of high quality polycyclic aromatic hydrocarbon adsorbent.
Liquid form is made in spirulina, is conducive to the polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon adsorbent absorption spirulina.
It is preferred that the method for polycyclic aromatic hydrocarbon adsorbent absorption spirulina extract, it is only necessary to which absorption can be completed in ultrasonic 10min, only
Need the i.e. separable polycyclic aromatic hydrocarbon adsorbent of magnet.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (4)
1. a kind of method of enriched removal polycyclic aromatic hydrocarbon, it is characterised in that: the following steps are included:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
The synthesis polycyclic aromatic hydrocarbon adsorbent method is as follows: synthesizing Fe using hydro-thermal method3O4Magnetic microsphere, then in pH8.0-9.0
Buffer in Fe is added3O4The Fe that dopamine wraps up is made after stirring 20-28h in magnetic microsphere and Dopamine hydrochloride3O4It is magnetic
Microballoon, after 35-45 DEG C of vacuum drying 10-14h, Fe that dopamine is wrapped up3O4Magnetic microsphere ultrasonic disperse in contain tri- second of 10mM
In the methanol solution of amine, the double sulfhydryl compounds of addition stir 16-20h at 25 DEG C and are modified, will be by the dopamine of modification
The Fe of package3O4Magnetic microsphere ultrasonic disperse is added 1- vinyl -3- octadecyl imidazoles bromide, adds azo in acetonitrile
Diethyl butyronitrile, under 65-75 DEG C of condition and nitrogen protection, mechanic whirl-nett reaction 16-20h, then rinsed with ethyl alcohol, it is dried in vacuo,
Obtain polycyclic aromatic hydrocarbon adsorbent；
It is described to synthesize Fe using hydro-thermal method3O4The method of magnetic microsphere is as follows:
Weigh 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol, magnetic agitation, until completely dissolved, is added
1.8gNaAc·3H2O, 0.5g polyethylene glycol continue after stirring 30min, move into the reaction kettle that 50ml liner is polytetrafluoroethylene (PTFE)
In, it after 200 DEG C of reaction 10h, is cooled to room temperature, by additional magnet sediment separate out, obtained magnetic microsphere is used largely respectively
Deionized water and dehydrated alcohol are washed to neutrality, 40 DEG C of vacuum drying 12h；
Step 2: polycyclic aromatic hydrocarbon adsorbent is enriched with polycyclic aromatic hydrocarbon；
The method of the polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon is as follows:
30mg polycyclic aromatic hydrocarbon adsorbent is weighed in beaker, is activated 2 times with acetonitrile, then is activated 2 times with water, it is to be removed that 50mL is added
The sample of polycyclic aromatic hydrocarbon, ultrasonic 10min make polycyclic aromatic hydrocarbon adsorbent sufficiently be enriched with polycyoalkane；Magnet is placed in beaker bottom,
It is adsorbed in polycyclic aromatic hydrocarbon adsorbent on magnet, supernatant is the sample for removing polycyclic aromatic hydrocarbon.
2. the method for enriched removal polycyclic aromatic hydrocarbon according to claim 1, it is characterised in that: synthesized in the step 1
The method of polycyclic aromatic hydrocarbon adsorbent is as follows:
Fe is synthesized using hydro-thermal method3O4Then Fe is added in the buffer of pH8.5 in magnetic microsphere3O4Magnetic microsphere and hydrochloric acid are more
The Fe of dopamine package is made in bar amine, stirring afterwards for 24 hours3O4Magnetic microsphere, after 40 DEG C of vacuum drying 12h, by dopamine package
Fe3O4Magnetic microsphere ultrasonic disperse is added double sulfhydryl compounds and stirs at 25 DEG C in the methanol solution containing 10mM triethylamine
18h is modified, by the Fe of the dopamine package by modification3O41- ethylene is added in acetonitrile in magnetic microsphere ultrasonic disperse
Base -3- octadecyl imidazoles bromide, adds azo diethyl butyronitrile, under 70 DEG C of conditions and nitrogen protection, mechanic whirl-nett reaction
18h is rinsed 3 times with ethyl alcohol, and 60 DEG C are dried in vacuum overnight, and obtain polycyclic aromatic hydrocarbon adsorbent.
3. the method for enriched removal polycyclic aromatic hydrocarbon according to claim 1, it is characterised in that: the enriched removal is more
The method of cycloaromatics is used to remove the polycyclic aromatic hydrocarbon in spirulina.
4. the method for enriched removal polycyclic aromatic hydrocarbon according to claim 1, it is characterised in that: the enriched removal is more
The method of cycloaromatics is used to remove the polycyclic aromatic hydrocarbon in ambient water.
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