CN106111070A - A kind of method removing polycyclic aromatic hydrocarbon - Google Patents
A kind of method removing polycyclic aromatic hydrocarbon Download PDFInfo
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- CN106111070A CN106111070A CN201610621741.0A CN201610621741A CN106111070A CN 106111070 A CN106111070 A CN 106111070A CN 201610621741 A CN201610621741 A CN 201610621741A CN 106111070 A CN106111070 A CN 106111070A
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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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
Abstract
The present invention relates to a kind of method removing polycyclic aromatic hydrocarbon.Comprise the following steps: step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；Described synthesis polycyclic aromatic hydrocarbon adsorbent is to utilize water heat transfer Fe3O4Magnetic microsphere, uses dopamine parcel Fe3O4Magnetic microsphere, and modify with double sulfhydryl compounds, prepare polycyclic aromatic hydrocarbon adsorbent；Step 2: polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon.Synthesizing polycyclic aromatic hydrocarbon adsorbent by sulfydryl alkene clicking chemistry method, for absorbing multiring aromatic hydrocarbon, adsorption efficiency is high, it is easy to separate, it is only necessary to Magnet gets final product separating adsorbent.
Description
Technical field
The present invention relates to a kind of method removing polycyclic aromatic hydrocarbon.
Background technology
Polycyclic aromatic hydrocarbon one class contains two or more phenyl ring or heterocycle with in wire, horn shape or tufted arrangement
, there is tobacco smoke, vehicle exhaust, petroleum chemicals and unburnt coal, wood in property or nonpolar organic compound
In the organic compound such as material, oil.Human body can be entered by food chain and breathing, can be enriched with in human body, thus affect gene table
Reach, and cause inducing cancer, mutagenesis, teratogenesis and other diseases, be classified as priority pollutants by countries in the world.
Spirulina has defying age, anti-hypoxia, resisting fatigue, radioprotective, blood fat reducing, blood pressure lowering, nourishing the liver are protected stomach and strengthened immunity
The effect of system, from the spirulina industry entry high-speed development period of 2005 to 2010 Nian Shi China, yield was sent out from more than 5000 tons
Exhibition is to 20,000 tons, and while pursuing high speed development, part producer is for reducing cost, and the requirement to quality reduces, due to spirulina
Primary growth, in various fresh water, sea water, is easily polluted by water body environment, after the polycyclic aromatic hydrocarbon in water body is absorbed by spirulina
Easily enrichment, thus human body is constituted a threat to.Polycyclic aromatic hydrocarbon in absorption spirulina needs high adsorption capacity, it is easy to the suction of separation
Attached dose；The method of the absorbing multiring aromatic hydrocarbon of report is used for adsorbing the polycyclic aromatic hydrocarbon in soil, air at present, and is applicable to absorption
In spirulina, the method for polycyclic aromatic hydrocarbon have not been reported.
Summary of the invention
The technical problem to be solved is: provide a kind of method removing polycyclic aromatic hydrocarbon, solves polycyclic aromatic hydrocarbon pair
The problem that human body constitutes a threat to.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: provide a kind of side removing polycyclic aromatic hydrocarbon
Method, comprises the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
Described synthesis polycyclic aromatic hydrocarbon adsorbent is to utilize water heat transfer Fe3O4Magnetic microsphere, uses dopamine parcel
Fe3O4Magnetic microsphere, and modify with double sulfhydryl compounds, prepare polycyclic aromatic hydrocarbon adsorbent；
Step 2: polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon.
The beneficial effects of the present invention is: the present invention is by sulfydryl-alkene clicking chemistry method synthesis polycyclic aromatic hydrocarbon adsorbent, mercapto
Base-alkene clicking chemistry is click on the one in chemical module, not only has that click chemistry reaction raw materials is abundant, reaction condition temperature
With, product stereo selectivity is good, productivity is high, post-reaction treatment and product separate simply, and byproduct of reaction is environmentally friendly；Should
Class reaction, without metallic catalyst, just may result from by base by light-initiated and thermal initiation, and reaction is simple, efficiently；At present, pass through
The report that glyoxaline ion liquid is modified magnetic nanometer surface by sulfydryl-alkene clicking chemistry method is the most fewer, particularly uses
Have not been reported in prepared polycyclic aromatic hydrocarbon adsorbent.Use the polycyclic aromatic hydrocarbon adsorbent polycyclic aromatic hydrocarbon prepared, adsorption efficiency
Height, owing to prepared polycyclic aromatic hydrocarbon adsorbent has magnetic, it is only necessary to Magnet gets final product separating adsorbent；Richness to 15 kinds of polycyclic aromatic hydrocarbons
Collection and elution requirement are optimized, and investigate its methodology parameter, and data show:, the method linear relationship and precision are good；With
The detection of polycyclic aromatic hydrocarbon in spirulina, method is quantitatively limited to 0.031-0.49 μ g/L；Except the response rate of naphthalene (NAP) is relatively low
(52.9%～66.7%) outward, the response rate of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Accompanying drawing explanation
Fig. 1 is Fe3O4、Fe3O4@DA and Fe3O4The XRD figure of@DA-IL；
Fig. 2 is Fe3O4@DA and Fe3O4The FT-IR figure of@DA-IL；
Fig. 3 is Fe3O4And Fe3O4The SEM figure of@DA-IL；
Fig. 4 is Fe3O4And Fe3O4The TEM figure of@DA-IL；
Fig. 5 is the Fe of various dose3O4The polycyclic aromatic hydrocarbon adsorbance of@DA-IL；
Fig. 6 is Fe3O4The@DA-IL response rate in the polycyclic aromatic hydrocarbon solution of variable concentrations；
Fig. 7 is Fe3O4The impact on adsorption efficiency of the time of@DA-IL absorbing multiring aromatic hydrocarbon.
Detailed description of the invention
By describing the technology contents of the present invention in detail, being realized purpose and effect, below in conjunction with embodiment and coordinate attached
Figure is explained.
The design of most critical of the present invention is: by sulfydryl-alkene clicking chemistry method synthesis polycyclic aromatic hydrocarbon adsorbent, be used for inhaling
Attached polycyclic aromatic hydrocarbon, adsorption efficiency is high, it is easy to separate, it is only necessary to Magnet gets final product separating adsorbent.
The present invention provides a kind of method removing polycyclic aromatic hydrocarbon, it is characterised in that: comprise the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
Described synthesis polycyclic aromatic hydrocarbon adsorbent is to utilize water heat transfer Fe3O4Magnetic microsphere, uses dopamine parcel
Fe3O4Magnetic microsphere, and modify with double sulfhydryl compounds, prepare polycyclic aromatic hydrocarbon adsorbent；
Step 2: polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon.
Knowable to foregoing description, the present invention is by sulfydryl-alkene clicking chemistry method synthesis polycyclic aromatic hydrocarbon adsorbent, sulfydryl-alkene
Click chemistry is click on the one in chemical module, not only has that click chemistry reaction raw materials is abundant, reaction condition gentle, product
Stereo selectivity is good, productivity is high, post-reaction treatment and product separate simple, and byproduct of reaction is environmentally friendly；Such reaction
Without metallic catalyst, just may result from by base by light-initiated and thermal initiation, reaction is simple, efficiently；At present, by sulfydryl-
The report that glyoxaline ion liquid is modified magnetic nanometer surface by alkene clicking chemistry method is the most fewer, especially for preparing
Polycyclic aromatic hydrocarbon adsorbent have not been reported.Using the polycyclic aromatic hydrocarbon adsorbent polycyclic aromatic hydrocarbon prepared, adsorption efficiency is high, due to
The polycyclic aromatic hydrocarbon adsorbent prepared has magnetic, it is only necessary to Magnet gets final product separating adsorbent；To the enrichment of 15 kinds of polycyclic aromatic hydrocarbons and wash
De-condition is optimized, and investigates its methodology parameter, and data show:, the method linear relationship and precision are good；For spiral
The detection of polycyclic aromatic hydrocarbon in algae, method is quantitatively limited to 0.031-0.49 μ g/L；The response rate relatively low (52.9% except naphthalene (NAP)
～66.7%) outward, the response rate of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Further, described step 1 synthesizes polycyclic aromatic hydrocarbon adsorbent method as follows:
Utilize water heat transfer Fe3O4Magnetic microsphere, then adds Fe in the buffer of pH8.0-9.03O4Magnetic microsphere
And dopamine hydrochloride, prepare the Fe of dopamine parcel after stirring 20-28h3O4Magnetic microsphere, 35-45 DEG C of vacuum drying 10-14h
After, the Fe that dopamine is wrapped up3O4Magnetic microsphere ultrasonic disperse, in the methanol solution containing 10mM triethylamine, adds double sulfydryl
Compound stirs 16-20h at 25 DEG C and modifies, by the Fe of the dopamine parcel through modifying3O4Magnetic microsphere ultrasonic disperse
In acetonitrile, add 1-vinyl-3-octadecyl imidazoles bromide, add azo diethyl butyronitrile, at 65-75 DEG C of condition and nitrogen
Under gas shielded, mechanic whirl-nett reaction 16-20h, the Fe of gained dopamine parcel3O4Magnetic microsphere uses alcohol flushing 2-5 time again, 55-
65 DEG C of dried in vacuum overnight, i.e. prepare polycyclic aromatic hydrocarbon adsorbent.
Seen from the above description, dopamine parcel Fe is used3O4Magnetic microsphere, and modify with double sulfhydryl compounds,
To product polycyclic aromatic hydrocarbon in spirulina is had the strongest absorbability.
Further, the method preferably synthesizing polycyclic aromatic hydrocarbon adsorbent in described step 1 is as follows:
Utilize water heat transfer Fe3O4Magnetic microsphere, then adds Fe in the buffer of pH8.53O4Magnetic microsphere and salt
Acid dopamine, prepares the Fe of dopamine parcel after stirring 24h3O4Magnetic microsphere, after 40 DEG C of vacuum drying 12h, wraps up dopamine
Fe3O4Magnetic microsphere ultrasonic disperse, in the methanol solution containing 10mM triethylamine, adds double sulfhydryl compound and stirs at 25 DEG C
Mix 18h to modify, by the Fe of the dopamine parcel through modifying3O4Magnetic microsphere ultrasonic disperse, in acetonitrile, adds 1-ethylene
Base-3-octadecyl imidazoles bromide, adds azo diethyl butyronitrile, under 70 DEG C of conditions and nitrogen are protected, and mechanic whirl-nett reaction
18h, with alcohol flushing 3 times, 60 DEG C of dried in vacuum overnight, i.e. prepares polycyclic aromatic hydrocarbon adsorbent.
Seen from the above description, optimize the synthesis condition of polycyclic aromatic hydrocarbon adsorbent further, obtain high-quality many cyclophanes
Hydrocarbon adsorbent, makes the adsorbent prepared have higher adsorption efficiency for polycyclic aromatic hydrocarbon.
Further, described water heat transfer Fe is utilized3O4The method of magnetic microsphere is as follows:
Weigh 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol.Magnetic agitation, until completely dissolved, adds
1.8gNaAc·3H2O, 0.5g Polyethylene Glycol, after continuing stirring 30min, moving into 50ml liner is the reactor of politef
In, after 200 DEG C of reaction 10h, it is cooled to room temperature, by additional Magnet sediment separate out.The magnetic microsphere obtained is respectively with a large amount of
Deionized water and absolute ethanol washing are to neutral, and 40 DEG C are vacuum dried 12h.
Seen from the above description, preferably water heat transfer Fe3O4The condition of the method for magnetic microsphere, obtains high-quality
Fe3O4Magnetic microsphere, the beneficially synthesis of high-quality polycyclic aromatic hydrocarbon adsorbent.
Further, the method for described removing polycyclic aromatic hydrocarbon is for removing the polycyclic aromatic hydrocarbon in spirulina.
For removing the polycyclic aromatic hydrocarbon in spirulina, the method for described removing polycyclic aromatic hydrocarbon also includes that preparing spirulina extracts
Liquid；It is described that to prepare spirulina extract method as follows:
Weigh 5.0g spirulina, add 25mL acetonitrile, shake on shaking table overnight after ultrasonic mixing, filter, will filter
To filtrate and the water spirulina extract of making water-acetonitrile mixed phase according to 1:2 mixing standby.
Using the polycyclic aromatic hydrocarbon in the polycyclic aromatic hydrocarbon adsorbent spirulina prepared, adsorption efficiency is high, due to prepared
Polycyclic aromatic hydrocarbon adsorbent has magnetic, it is only necessary to Magnet can in spirulina extract separating adsorbent；To 15 kinds of polycyclic aromatic hydrocarbons
Enrichment and elution requirement be optimized, investigate its methodology parameter, data show:, the method linear relationship and precision are good
Good；The detection of polycyclic aromatic hydrocarbon in spirulina, method is quantitatively limited to 0.031-0.49 μ g/L；The response rate except naphthalene (NAP)
Relatively low (52.9%～66.7%) outward, the response rate of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Sample is made the polycyclic aromatic hydrocarbon in aqueous phase liquid form, beneficially polycyclic aromatic hydrocarbon adsorbent aqueous phase.
Further, the method for described removing polycyclic aromatic hydrocarbon is for removing the polycyclic aromatic hydrocarbon in Environmental Water.
Water, as the requisite resource of human lives, uses the polycyclic aromatic hydrocarbon adsorbent energy active adsorption that the present invention relates to
Polycyclic aromatic hydrocarbon in Environmental Water, prevents the polycyclic aromatic hydrocarbon in water from affecting human health.
Further, in described step 2, the method for polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon is as follows:
Weigh 30mg polycyclic aromatic hydrocarbon adsorbent in beaker, activate 2 times with acetonitrile, then activate 2 times with water, add 50mL and treat
Remove the sample of polycyclic aromatic hydrocarbon, ultrasonic 10min, make polycyclic aromatic hydrocarbon adsorbent fully be enriched with polycyoalkane；Magnet is placed in beaker
Bottom, makes polycyclic aromatic hydrocarbon adsorbent on Magnet, and supernatant is the sample removing polycyclic aromatic hydrocarbon.
Seen from the above description, the preferred method of polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon adsorbent sample, it is only necessary to ultrasonic
10min can complete absorption, it is only necessary to Magnet the most separable polycyclic aromatic hydrocarbon adsorbent.
Embodiment 1
1, a kind of remove the method for polycyclic aromatic hydrocarbon in spirulina, comprise the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
Utilize water heat transfer Fe3O4Magnetic microsphere, weighs 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol.Magnetic force
Stirring, until completely dissolved, adds 1.8gNaAc 3H2O, 0.5g Polyethylene Glycol, after continuing stirring 30min, moves into 50ml
Liner is in the reactor of politef, after 200 DEG C of reaction 10h, is cooled to room temperature, by additional Magnet sediment separate out.
The magnetic microsphere obtained is the most neutral with a large amount of deionized waters and absolute ethanol washing respectively, 40 DEG C of vacuum drying 12h.
Then in the buffer of pH8.5, add dopamine, prepared dopamine parcel particle after mechanical agitation 24h, 40 DEG C
After vacuum drying 12h, by its ultrasonic disperse in the methanol solution of 10mM triethylamine, add double sulfhydryl compound at normal temperature condition
Lower mechanical agitation 18h is modified, and by the particle ultrasonic disperse through modifying in acetonitrile, adds 1-vinyl-3-octadecane
Base imidazoles bromide, adds azo diethyl butyronitrile, at 70 DEG C of conditions and N2Under protection, mechanic whirl-nett reaction 18h, uses alcohol flushing
3 times, 60 DEG C of dried in vacuum overnight, i.e. prepare polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL。
Prepare spirulina extract；
Weigh 5.0g spirulina, add 25mL acetonitrile, shake on shaking table overnight after ultrasonic mixing, filter, will filter
To filtrate and the water spirulina extract of making water-acetonitrile mixed phase according to 1:2 mixing standby.
Step 2: the polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon adsorbent enrichment spirulina extract；
Weigh 30mg polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL, in beaker, activates 2 times with acetonitrile, then activates 2 times with water,
Add 50mL spirulina extract, ultrasonic 10min, make polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL is fully enriched with spirulina extract
In polycyoalkane；Magnet is placed in beaker bottom, makes Fe3O4@DA-IL is adsorbed on Magnet, and supernatant is the many cyclophanes of removing
The spirulina extract of hydrocarbon.
2, a kind of remove the method for polycyclic aromatic hydrocarbon in Environmental Water, comprise the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
Utilize water heat transfer Fe3O4Magnetic microsphere, weighs 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol.Magnetic force
Stirring, until completely dissolved, adds 1.8gNaAc 3H2O, 0.5g Polyethylene Glycol, after continuing stirring 30min, moves into 50ml
Liner is in the reactor of politef, after 200 DEG C of reaction 10h, is cooled to room temperature, by additional Magnet sediment separate out.
The magnetic microsphere obtained is the most neutral with a large amount of deionized waters and absolute ethanol washing respectively, 40 DEG C of vacuum drying 12h.
Then in the buffer of pH8.5, add dopamine, prepared dopamine parcel particle after mechanical agitation 24h, 40 DEG C
After vacuum drying 12h, by its ultrasonic disperse in the methanol solution of 10mM triethylamine, add double sulfhydryl compound at normal temperature condition
Lower mechanical agitation 18h is modified, and by the particle ultrasonic disperse through modifying in acetonitrile, adds 1-vinyl-3-octadecane
Base imidazoles bromide, adds azo diethyl butyronitrile, at 70 DEG C of conditions and N2Under protection, mechanic whirl-nett reaction 18h, uses alcohol flushing
3 times, 60 DEG C of dried in vacuum overnight, i.e. prepare polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL。
Environmental Water brown reagent bottle cold preservation, first stands before mensuration, discards precipitate, takes after 0.45 μm membrane filtration
50mL, 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, in beaker, activates 2 times with acetonitrile, then activates 2 times with water,
Add 50mL Environmental Water, ultrasonic 10min, make polycyclic aromatic hydrocarbon adsorbent Fe3O4Polynaphthene in@DA-IL abundant enrichment environment water
Hydrocarbon；Magnet is placed in beaker bottom, makes Fe3O4@DA-IL is adsorbed on Magnet, and supernatant is the environment removing polycyclic aromatic hydrocarbon
Water.
2, the material characterization of above-mentioned polycyclic aromatic hydrocarbon adsorbent:
Such as Fig. 1, with X-ray powder diffractometer to prepared Fe3O4, Fe3O4@DA and Fe3O4@DA-IL is analyzed.
As shown in Figure 1, the Fe of preparation3O4And Fe3O4The XRD diffraction maximum of@DA-IL all occurs in that Fe3O46 characteristic peaks, respectively correspondence
Fe3O4(220), (331), (400), (422), (511) and (440) feature crystal face, show Fe3O4Be successfully prepared and after repair
During decorations, magnetic core does not change.
Fig. 2 is Fe3O4@DA and Fe3O4The infrared spectrogram of@DA-IL magnetic microsphere.In figure, 1280cm-1 is alkyl C-N
Stretching vibration absworption peak, 1429cm-1It is CH3Asymmetric stretching absorption peak, 1621cm-1Place is the stretching vibration of C=C and C=N
Absworption peak, 2923cm-1It is CH2Asymmetric stretching absorption peak, illustrate that 1-vinyl-3-octadecyl imidazoles bromide is combined in
Fe3O4@DA surface.
Fig. 3 is Fe3O4And Fe3O4The SEM figure of@DA-IL magnetic microsphere.From figure 3, it can be seen that Fe3O4For spheroidal particle,
It is uniformly dispersed.Cladding [VC18Im] after Br, particle diameter has increased, and nanoparticle surface forms light irregular shell, and particle divides
Dissipate property good.
Fig. 4 is TEM figure, it can be seen that Fe3O4For spheroidal, granule is uniformly and good dispersion, the Fe after parcel3O4@DA-
IL is spherical constant, and shell thickness is than more uniform about 50nm.
The Fe of unmodified3O4Saturation magnetization is up to 84emu/g, is down to 46emu/g after dopamine wraps up, cladding
After dodecyl long-chain, saturation magnetization slightly rises to 53emu/g, and this is owing to when dopamine wraps up, a part is many
Bar amine autohemagglutination synthesizes non-magnetic granule, reduces the average magnetization of lapping, non-magnetic many when last modification
Bar amine polymer is removed.The intensity of magnetization of synthetic material still falls within high saturation magnetization, and this is beneficial in enrichment
Rear quickly Magneto separate.
3, the condition optimizing of above-mentioned polycyclic aromatic hydrocarbon adsorbent polycyclic aromatic hydrocarbon:
Owing to polycyclic aromatic hydrocarbon is the compound that a series of structure is similar, character is close, therefore for simplifying data analysis step,
Select higher PHE, ANT, FLT and PYR standard mixed solution of its medium sensitivity herein and carry out magnetic Solid-Phase Extraction for analyzing object
The optimization of condition, investigates adsorbent amount, extraction time, eluant kind with the standard mixed solution of 50mL10 μ g/L and washes
The de-time impact on effect of extracting.
Weigh the Fe of 10mg, 20mg, 30mg, 50mg, 100mg respectively3O4@DA-IL tetra-kinds of polycyclic aromatic hydrocarbons of 50mL10 μ g/L
Overnight, then abandoning supernatant under outside magnetic field, first washes with water mixed mark solution soaking, then with on acetonitrile eluting magnetic nanometer
Object be measured, result is as shown in Figure 5.It can be seen that along with the increase of adsorbent amount, elution amount is gradually
Increasing, when adsorbent amount is at more than 30mg, polycyclic aromatic hydrocarbon elution amount basically reaches stable, and quantity of sorbent continues to increase, and washes
De-amount is not apparent from change.
Weigh the magnetic microsphere of 30mg, respectively with 50mL0.01, the polycyclic aromatic hydrocarbon of 0.02,0.2,1,10,50,100 μ g/L
Overnight, then same treatment, result is shown in Fig. 6 to mixed mark solution soaking, it can be seen that magnetic nanometer material is at object
Concentration is at 60%-80% less than enriching and recovering rate during 0.2 μ g/L, this is because adsorbing material and object when concentration is low
Contact probability is relatively low, needs longer equilibration time, but bioaccumulation efficiency remains to reach 60% enrichment material described above to many
The specificity of PAH is good, this is because: the Fe of nanostructured3O4The outer surface of@DA-IL is long-pending very big, and its surface is containing abundant
Benzene radicals, long alkane chain makes the intermolecular force between the hydrophobic group of material and polycyclic aromatic hydrocarbon strengthen, simultaneously
Phenyl ring on chain and glyoxaline structure easily and the phenyl ring formation Л-Л conjugated electrons cloud of polycyclic aromatic hydrocarbon thus be adsorbed in Fe3O4@
DA-IL surface；Bioaccumulation efficiency when polycyclic aromatic hydrocarbon concentration is at 0.2-10 μ g/L is best, and the response rate, at 75-108%, works as target
When substrate concentration is more than 50 μ g/L, the response rate of adsorbed target thing begins to decline, and points out now adsorbance to reach saturated.
Fe3O4The time of@DA-IL absorbing multiring aromatic hydrocarbon directly affects adsorption efficiency, owing to the magnetic of adsorbent itself makes
Adsorbent adsorbs mutually conglomeration and sedimentation causes adsorption efficiency to reduce, and therefore adsorbing material ultrasonic disperse in the solution is made material
Material fully can be suspended in sample solution and adsorb, investigate different adsorption time (5min, 10min, 15min, 20min and
25min) on the impact of adsorption effect as shown in Figure 7.It can be seen that along with the increase adsorbance of adsorption time also increases
Greatly, when adsorption time is 10min, absorption reaches steady statue, and adsorption time extends, and adsorbance is basically unchanged.
In sum, the beneficial effects of the present invention is: the present invention is by sulfydryl-alkene clicking chemistry method synthesis polycyclic aromatic hydrocarbon
Adsorbent, sulfydryl-alkene clicking chemistry is click on the one in chemical module, not only has click chemistry reaction raw materials abundant, anti-
Answer mild condition, product stereo selectivity is good, productivity is high, post-reaction treatment and product separate simple, and byproduct of reaction is to ring
Border is friendly；Such reaction, without metallic catalyst, just may result from by base by light-initiated and thermal initiation, and reaction is simple, efficiently；
At present, the report that glyoxaline ion liquid is modified magnetic nanometer surface by sulfydryl-alkene clicking chemistry method is the most fewer,
Have not been reported especially for prepared polycyclic aromatic hydrocarbon adsorbent.Use in the polycyclic aromatic hydrocarbon adsorbent spirulina prepared
Polycyclic aromatic hydrocarbon, adsorption efficiency is high, owing to prepared polycyclic aromatic hydrocarbon adsorbent has magnetic, it is only necessary to Magnet can extract at spirulina
Separating adsorbent in liquid；Enrichment and elution requirement to 15 kinds of polycyclic aromatic hydrocarbons are optimized, and investigate its methodology parameter, and data show
Show: the method linear relationship and precision are good；The detection of polycyclic aromatic hydrocarbon in spirulina, method is quantitatively limited to 0.031-
0.49μg/L；In addition to naphthalene (NAP), the response rate of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Use dopamine parcel Fe3O4Magnetic microsphere, and modify with double sulfhydryl compounds, the product obtained is to spiral
In algae, polycyclic aromatic hydrocarbon has the strongest absorbability.
Optimize the synthesis condition of polycyclic aromatic hydrocarbon adsorbent further, obtain high-quality polycyclic aromatic hydrocarbon adsorbent, make to prepare
Adsorbent for the polycyclic aromatic hydrocarbon in spirulina, there is higher adsorption efficiency.
Preferably water heat transfer Fe3O4The condition of the method for magnetic microsphere, obtains high-quality Fe3O4Magnetic microsphere, favorably
Synthesis in high-quality polycyclic aromatic hydrocarbon adsorbent.
Optimize water heat transfer Fe further3O4The condition of the method for magnetic microsphere, obtains higher-quality Fe3O4Magnetic
Microsphere, is more beneficial for the synthesis of high-quality polycyclic aromatic hydrocarbon adsorbent.
Spirulina is made liquid form, beneficially the polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon adsorbent spirulina.
The preferably method of polycyclic aromatic hydrocarbon adsorbent spirulina extract, it is only necessary to ultrasonic 10min can complete absorption, only
Need Magnet the most separable polycyclic aromatic hydrocarbon adsorbent.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every utilize this
The equivalents that bright description is made, or directly or indirectly it is used in relevant technical field, the most in like manner it is included in this
In bright scope of patent protection.
Claims (8)
1. the method removing polycyclic aromatic hydrocarbon, it is characterised in that: comprise the following steps:
Step 1: synthesis polycyclic aromatic hydrocarbon adsorbent；
Described synthesis polycyclic aromatic hydrocarbon adsorbent is to utilize water heat transfer Fe3O4Magnetic microsphere, uses dopamine parcel Fe3O4Magnetic
Microsphere, and modify with double sulfhydryl compounds, prepare polycyclic aromatic hydrocarbon adsorbent；
Step 2: polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon.
The method of removing polycyclic aromatic hydrocarbon the most according to claim 1, it is characterised in that: described step 1 synthesizes many cyclophanes
Hydrocarbon adsorbent method is as follows:
Utilize water heat transfer Fe3O4Magnetic microsphere, then adds Fe in the buffer of pH8.0-9.03O4Magnetic microsphere and salt
Acid dopamine, prepares the Fe of dopamine parcel after stirring 20-28h3O4Magnetic microsphere, after 35-45 DEG C of vacuum drying 10-14h, will
The Fe of dopamine parcel3O4Magnetic microsphere ultrasonic disperse, in the methanol solution containing 10mM triethylamine, adds double sulfhydryl compound
At 25 DEG C, stir 16-20h modify, by the Fe of the dopamine parcel through modifying3O4Magnetic microsphere ultrasonic disperse is in acetonitrile
In, add 1-vinyl-3-octadecyl imidazoles bromide, add azo diethyl butyronitrile, protect in 65-75 DEG C of condition and nitrogen
Under, mechanic whirl-nett reaction 16-20h, the Fe of gained dopamine parcel3O4Magnetic microsphere uses alcohol flushing 2-5 time again, and 55-65 DEG C true
Sky is dried overnight, and i.e. prepares polycyclic aromatic hydrocarbon adsorbent.
The method of removing polycyclic aromatic hydrocarbon the most according to claim 1, it is characterised in that: described step 1 preferably synthesizes
The method of polycyclic aromatic hydrocarbon adsorbent is as follows:
Utilize water heat transfer Fe3O4Magnetic microsphere, then adds Fe in the buffer of pH8.53O4Magnetic microsphere and hydrochloric acid are many
Bar amine, prepares the Fe of dopamine parcel after stirring 24h3O4Magnetic microsphere, after 40 DEG C of vacuum drying 12h, wraps up dopamine
Fe3O4Magnetic microsphere ultrasonic disperse, in the methanol solution containing 10mM triethylamine, adds double sulfhydryl compound and stirs at 25 DEG C
18h modifies, by the Fe of the dopamine parcel through modifying3O4Magnetic microsphere ultrasonic disperse, in acetonitrile, adds 1-ethylene
Base-3-octadecyl imidazoles bromide, adds azo diethyl butyronitrile, under 70 DEG C of conditions and nitrogen are protected, and mechanic whirl-nett reaction
18h, with alcohol flushing 3 times, 60 DEG C of dried in vacuum overnight, i.e. prepares polycyclic aromatic hydrocarbon adsorbent.
The method of removing polycyclic aromatic hydrocarbon the most according to claim 1 and 2, it is characterised in that: described utilize water heat transfer
Fe3O4The method of magnetic microsphere is as follows:
Weigh 0.675gFeCl3·6H2O is dissolved in 20mL ethylene glycol.Magnetic agitation, until completely dissolved, adds
1.8gNaAc·3H2O, 0.5g Polyethylene Glycol, after continuing stirring 30min, moving into 50ml liner is the reactor of politef
In, after 200 DEG C of reaction 10h, it is cooled to room temperature, by additional Magnet sediment separate out.The magnetic microsphere obtained is respectively with a large amount of
Deionized water and absolute ethanol washing are to neutral, and 40 DEG C are vacuum dried 12h.
The method of removing polycyclic aromatic hydrocarbon the most according to claim 1, it is characterised in that: the method for described removing polycyclic aromatic hydrocarbon
For removing the polycyclic aromatic hydrocarbon in spirulina.
The method removing polycyclic aromatic hydrocarbon the most according to claim 1 or 5, it is characterised in that: described removing polycyclic aromatic hydrocarbon
Method also includes preparing spirulina extract for removing the polycyclic aromatic hydrocarbon in spirulina；Described prepare spirulina extract method
As follows:
Weigh 5.0g spirulina, add 25mL acetonitrile, shake on shaking table overnight after ultrasonic mixing, filter, by be filtrated to get
The spirulina extract that filtrate makes water-acetonitrile mixed phase with water according to 1:2 mixing is standby.
The method of removing polycyclic aromatic hydrocarbon the most according to claim 1, it is characterised in that: the method for described removing polycyclic aromatic hydrocarbon
For removing the polycyclic aromatic hydrocarbon in Environmental Water.
The method of removing polycyclic aromatic hydrocarbon the most according to claim 1, it is characterised in that: in described step 2, polycyclic aromatic hydrocarbon is inhaled
The method of attached dose of enrichment polycyclic aromatic hydrocarbon is as follows:
Weigh 30mg polycyclic aromatic hydrocarbon adsorbent in beaker, activate 2 times with acetonitrile, then activate 2 times with water, add 50mL to be removed
The sample of polycyclic aromatic hydrocarbon, ultrasonic 10min, make polycyclic aromatic hydrocarbon adsorbent fully be enriched with polycyoalkane；Magnet is placed in beaker bottom,
Making polycyclic aromatic hydrocarbon adsorbent on Magnet, supernatant is the sample removing polycyclic aromatic hydrocarbon.
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| CN201810927478.7A CN108940216B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in spirulina |
| CN201810927213.7A CN108927114B (en) | 2016-08-01 | 2016-08-01 | Method for efficiently adsorbing polycyclic aromatic hydrocarbon in spirulina |
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| CN109940029A (en) * | 2019-04-18 | 2019-06-28 | 重庆大学 | The method for being catalyzed polycyclic aromatic hydrocarbon in subcritical water oxidation degradation incineration of refuse flyash |
| CN114130374A (en) * | 2021-11-04 | 2022-03-04 | 华南理工大学 | Application of magnetic carboxylated covalent organic framework material as magnetic solid-phase extraction adsorbent |
| CN114433034A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Super-crosslinked polymer modified magnetic nanoparticles and preparation method and application thereof |
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| CN106111070B (en) | 2018-09-11 |
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| CN108940215A (en) | 2018-12-07 |
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