CN106111070B - A method of removing polycyclic aromatic hydrocarbon - Google Patents
A method of removing polycyclic aromatic hydrocarbon Download PDFInfo
- Publication number
- CN106111070B CN106111070B CN201610621741.0A CN201610621741A CN106111070B CN 106111070 B CN106111070 B CN 106111070B CN 201610621741 A CN201610621741 A CN 201610621741A CN 106111070 B CN106111070 B CN 106111070B
- Authority
- CN
- China
- Prior art keywords
- aromatic hydrocarbon
- polycyclic aromatic
- adsorbent
- magnetic microsphere
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000003463 adsorbent Substances 0.000 claims abstract description 85
- 239000004005 microsphere Substances 0.000 claims abstract description 44
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 59
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 46
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 235000016425 Arthrospira platensis Nutrition 0.000 claims description 25
- 240000002900 Arthrospira platensis Species 0.000 claims description 25
- 229960003638 dopamine Drugs 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229940082787 spirulina Drugs 0.000 claims description 22
- -1 1- vinyl -3- octadecyl imidazoles bromides Chemical class 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 235000003724 spirulina extract Nutrition 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 3
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 3
- 150000001412 amines Chemical class 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000001311 chemical methods and process Methods 0.000 abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000011084 recovery Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- 238000010828 elution Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000005389 magnetism Effects 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007867 post-reaction treatment Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 231100000405 induce cancer Toxicity 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—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
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Genetics & Genomics (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Tropical Medicine & Parasitology (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- Virology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of methods removing polycyclic aromatic hydrocarbon.Include the following steps：Step 1：Synthesize 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 is used in combination double sulfhydryl compounds to be modified, 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
Technical field
The present invention relates to a kind of methods removing polycyclic aromatic hydrocarbon.
Background technology
Polycyclic aromatic hydrocarbon is during one kind is arranged containing two or more phenyl ring or heterocycle with linear, horn shape or tufted
Property or nonpolar organic compound, there are tobacco smoke, vehicle exhaust, petroleum chemicals and unburnt coal, 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, radioresistance, 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, seawater, is easy to be polluted by water body environment, 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 the polycyclic aromatic hydrocarbon in soil, air, and suitable for absorption
The method of polycyclic aromatic hydrocarbon has not been reported in spirulina.
Invention content
The technical problem to be solved by the present invention is to：A kind of method removing polycyclic aromatic hydrocarbon is provided, polycyclic aromatic hydrocarbon pair is solved
The problem of human body constitutes a threat to.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of side removing polycyclic aromatic hydrocarbon is provided
Method includes the following steps：
Step 1：Synthesize 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 is used in combination double sulfhydryl compounds to be modified, polycyclic aromatic hydrocarbon adsorbent is made；
Step 2：Polycyclic aromatic hydrocarbon adsorbent is enriched with 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 click chemistry mould one kind in the block, not only there are click chemistry reaction raw materials to enrich, reaction condition temperature
It is good with product stereoselectivity, yield is high, post-reaction treatment and product detach 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 thermal initiation, and reaction is simply, efficiently；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 relatively low
(52.9%~66.7%) outside, the rate of recovery of other 14 kinds of polycyclic aromatic hydrocarbons is 78.4%-107.1%.
Description of the drawings
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 hydrocarbons to adsorption efficiency.
Specific implementation mode
To explain the technical content, the achieved purpose and the effect of the present invention in detail, below in conjunction with embodiment and coordinate attached
Figure is explained.
The design of most critical of the present invention is：Polycyclic aromatic hydrocarbon adsorbent is synthesized by sulfydryl-alkene clicking chemistry method, for inhaling
Attached polycyclic aromatic hydrocarbon, adsorption efficiency is high, is easily isolated, it is only necessary to which magnet can separating adsorbent.
The present invention provides a kind of method removing polycyclic aromatic hydrocarbon, it is characterised in that：Include the following steps：
Step 1：Synthesize 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 is used in combination double sulfhydryl compounds to be modified, 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 click chemistry mould one kind in the block, 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 thermal 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, is especially used to be 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 relatively low (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 solution 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 triethylamines 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 bromides are added, azo diethyl butyronitrile are 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 is used in combination double sulfhydryl compounds to be modified, is obtained
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 solution of pH8.5 in magnetic microsphere3O4Magnetic microsphere and salt
The Fe of dopamine package is made in sour dopamine, stirring afterwards for 24 hours3O4Magnetic microsphere wraps up dopamine after 40 DEG C are dried in vacuo 12h
Fe3O4Magnetic microsphere ultrasonic disperse is added double sulfhydryl compounds and is stirred at 25 DEG C in the methanol solution containing 10mM triethylamines
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 bromides, add 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 liners are 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 a large amount of respectively
Deionized water and absolute ethyl 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 removing polycyclic aromatic hydrocarbon is used to remove the polycyclic aromatic hydrocarbon in spirulina.
It further includes preparing spirulina extraction that the method for removing polycyclic aromatic hydrocarbon, which is used to remove the polycyclic aromatic hydrocarbon in spirulina,
Liquid；It is described that prepare spirulina extract method as follows：
5.0g spirulinas are weighed, 25mL acetonitriles are added, are shaken on shaking table after ultrasonic mixing overnight, filtering will filter
The filtrate arrived is with water according to 1:The spirulina extract that water-acetonitrile mixed phase is made in 2 mixings is spare.
Polycyclic aromatic hydrocarbon in spirulina is adsorbed using polycyclic aromatic hydrocarbon adsorbent obtained, 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)
Relatively low (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 removing 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 adsorbents are weighed in beaker, are activated 2 times with acetonitrile, then are 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 fully be enriched with polycyoalkane；Magnet is placed in beaker
Bottom makes polycyclic aromatic hydrocarbon adsorbent be adsorbed 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 removing polycyclic aromatic hydrocarbon in spirulina, includes the following steps：
Step 1：Synthesize 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 absolute ethyl alcohol to neutrality respectively, 40 DEG C of vacuum drying 12h.
Then it is added dopamine in the buffer solution of pH8.5, mechanical agitation is made dopamine and wraps up particle afterwards for 24 hours, 40 DEG C
After being dried in vacuo 12h, by its ultrasonic disperse in the methanol solution of 10mM triethylamines, double sulfhydryl compounds are added in normal temperature condition
Lower mechanical agitation 18h is modified, and by the particle ultrasonic disperse by modification in acetonitrile, 1- vinyl -3- octadecanes are 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 spirulinas are weighed, 25mL acetonitriles are added, are shaken on shaking table after ultrasonic mixing overnight, filtering will filter
The filtrate arrived is with water according to 1:The spirulina extract that water-acetonitrile mixed phase is made in 2 mixings is spare.
Step 2：Polycyclic aromatic hydrocarbon adsorbent is enriched with the polycyclic aromatic hydrocarbon in spirulina extract；
Weigh 30mg polycyclic aromatic hydrocarbon adsorbents Fe3O4@DA-IL are activated 2 times in beaker with acetonitrile, then are activated 2 times with water,
50mL spirulina extracts are added, ultrasonic 10min makes polycyclic aromatic hydrocarbon adsorbent Fe3O4@DA-IL are fully enriched with spirulina extract
In polycyoalkane；Magnet is placed in beaker bottom, makes Fe3O4@DA-IL are adsorbed on magnet, and supernatant is to remove polycyclic virtue
The spirulina extract of hydrocarbon.
2, a kind of method removing polycyclic aromatic hydrocarbon in ambient water, includes the following steps：
Step 1：Synthesize 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 absolute ethyl alcohol to neutrality respectively, 40 DEG C of vacuum drying 12h.
Then it is added dopamine in the buffer solution of pH8.5, mechanical agitation is made dopamine and wraps up particle afterwards for 24 hours, 40 DEG C
After being dried in vacuo 12h, by its ultrasonic disperse in the methanol solution of 10mM triethylamines, double sulfhydryl compounds are added in normal temperature condition
Lower mechanical agitation 18h is modified, and by the particle ultrasonic disperse by modification in acetonitrile, 1- vinyl -3- octadecanes are 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 measuring, is discarded sediment, taken after 0.45 μm of membrane filtration
50mL, it is to be measured.
Step 2：Polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon adsorbent enrichment environment water；
Weigh 30mg polycyclic aromatic hydrocarbon adsorbents Fe3O4@DA-IL are activated 2 times in beaker with acetonitrile, then are activated 2 times with water,
50mL ambient waters are 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 are 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 are analyzed.
As shown in Figure 1, the Fe of preparation3O4And Fe3O4There is Fe in the XRD diffraction maximums of@DA-IL3O46 characteristic peaks, correspond to respectively
Fe3O4(220), (331), (400), (422), (511) and (440) feature crystal face, show Fe3O4It is successfully prepared and is repaiied after
Magnetic core does not change during decorations.
Fig. 2 is Fe3O4@DA and Fe3O4The infrared spectrogram of@DA-IL magnetic microspheres.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 bromides are incorporated in
Fe3O4The surfaces@DA.
Fig. 3 is Fe3O4And Fe3O4The SEM of@DA-IL magnetic microspheres schemes.From figure 3, it can be seen that Fe3O4For spheric granules,
It is uniformly dispersed.Coat [VC18Im] after Br, grain 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 figures, it can be seen that Fe3O4For spheroidal, particle uniformly and good dispersion, the Fe after package3O4@DA-
IL spherical shapes are 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 when dopamine wraps up, a part is more
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,
It is that analysis object carries out magnetic solid phase extraction to select PHE, ANT, FLT and PYR standard mixed solution wherein in higher sensitivity herein
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, the results are shown in Figure 5.It can be seen from the figure that with the increase of adsorbent amount, elution amount is gradual
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
A concentration of enriching and recovering rate when being less than 0.2 μ g/L is in 60%-80%, this is because sorbing 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 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 makes the intermolecular force between the hydrophobic grouping of material and polycyclic aromatic hydrocarbon enhance, simultaneously
Phenyl ring and glyoxaline structure on chain are easily and the phenyl ring of polycyclic aromatic hydrocarbon forms Л-Л conjugated electrons clouds to be adsorbed in Fe3O4@
The surfaces 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 hydrocarbons 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 sorbing material
Material can fully 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 click chemistry mould one kind in the block, 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 thermal initiation, and reaction is simply, efficiently；
Currently, the report by sulfydryl-alkene clicking chemistry method by glyoxaline ion liquid modification to magnetic nanometer surface is also fewer,
It is especially used to that polycyclic aromatic hydrocarbon adsorbent to be made and has not been reported.It is adsorbed in spirulina using polycyclic aromatic hydrocarbon adsorbent obtained
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 is used in combination double sulfhydryl compounds to be modified, and 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.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every 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 (7)
1. a kind of method removing polycyclic aromatic hydrocarbon, it is characterised in that：Include the following steps：
Step 1：Synthesize polycyclic aromatic hydrocarbon adsorbent；
The synthesis polycyclic aromatic hydrocarbon adsorbent method is as follows：Fe is synthesized using hydro-thermal method3O4Magnetic microsphere, then in pH8.0-9.0
Buffer solution 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 is dried in vacuo 10-14h, by the Fe of dopamine package3O4Magnetic microsphere ultrasonic disperse is in containing 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 bromides, adds azo in acetonitrile
Diethyl butyronitrile, under 65-75 DEG C of condition and nitrogen protection, mechanic whirl-nett reaction 16-20h, then rinsed 2-5 times with ethyl alcohol, 55-65
It DEG C is dried in vacuum overnight, obtains polycyclic aromatic hydrocarbon adsorbent；
Step 2：Polycyclic aromatic hydrocarbon adsorbent is enriched with polycyclic aromatic hydrocarbon.
2. the method according to claim 1 for removing polycyclic aromatic hydrocarbon, it is characterised in that：Polycyclic virtue is synthesized in the step 1
The method of hydrocarbon adsorbent is as follows：
Fe is synthesized using hydro-thermal method3O4Then Fe is added in the buffer solution 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 are dried in vacuo 12h, by dopamine package
Fe3O4Magnetic microsphere ultrasonic disperse is added double sulfhydryl compounds and is stirred at 25 DEG C in the methanol solution containing 10mM triethylamines
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 bromides, add 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 according to claim 1 for removing polycyclic aromatic hydrocarbon, it is characterised in that：It is described to synthesize Fe using hydro-thermal method3O4
The 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 liners are 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 a large amount of respectively
Deionized water and absolute ethyl alcohol are washed to neutrality, 40 DEG C of vacuum drying 12h.
4. the method according to claim 1 for removing polycyclic aromatic hydrocarbon, it is characterised in that：The method for removing polycyclic aromatic hydrocarbon
For removing the polycyclic aromatic hydrocarbon in spirulina.
5. the method according to claim 1 or 4 for removing polycyclic aromatic hydrocarbon, it is characterised in that：The removing polycyclic aromatic hydrocarbon
The polycyclic aromatic hydrocarbon that method is used to remove in spirulina further includes preparing spirulina extract；It is described to prepare spirulina extract method
It is as follows：
5.0g spirulinas are weighed, 25mL acetonitriles are added, are shaken on shaking table after ultrasonic mixing overnight, filtering, by what is be obtained by filtration
Filtrate is with water according to 1:The spirulina extract that water-acetonitrile mixed phase is made in 2 mixings is spare.
6. the method according to claim 1 for removing polycyclic aromatic hydrocarbon, it is characterised in that：The method for removing polycyclic aromatic hydrocarbon
For removing the polycyclic aromatic hydrocarbon in ambient water.
7. the method according to claim 1 for removing polycyclic aromatic hydrocarbon, it is characterised in that：
The method of polycyclic aromatic hydrocarbon adsorbent enrichment polycyclic aromatic hydrocarbon is as follows in the step 2：
30mg polycyclic aromatic hydrocarbon adsorbents are weighed in beaker, are activated 2 times with acetonitrile, then are 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 fully be enriched with polycyoalkane；Magnet is placed in beaker bottom,
Polycyclic aromatic hydrocarbon adsorbent is set to be adsorbed on magnet, supernatant is the sample for removing polycyclic aromatic hydrocarbon.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610621741.0A CN106111070B (en) | 2016-08-01 | 2016-08-01 | A method of removing polycyclic aromatic hydrocarbon |
| CN201810927445.2A CN108940215B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in enrichment manner |
| CN201810927213.7A CN108927114B (en) | 2016-08-01 | 2016-08-01 | Method for efficiently adsorbing polycyclic aromatic hydrocarbon in spirulina |
| CN201810927478.7A CN108940216B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in spirulina |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610621741.0A CN106111070B (en) | 2016-08-01 | 2016-08-01 | A method of removing polycyclic aromatic hydrocarbon |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810927445.2A Division CN108940215B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in enrichment manner |
| CN201810927478.7A Division CN108940216B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in spirulina |
| CN201810927213.7A Division CN108927114B (en) | 2016-08-01 | 2016-08-01 | Method for efficiently adsorbing polycyclic aromatic hydrocarbon in spirulina |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106111070A CN106111070A (en) | 2016-11-16 |
| CN106111070B true CN106111070B (en) | 2018-09-11 |
Family
ID=57254589
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810927445.2A Expired - Fee Related CN108940215B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in enrichment manner |
| CN201810927478.7A Expired - Fee Related CN108940216B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in spirulina |
| CN201610621741.0A Expired - Fee Related CN106111070B (en) | 2016-08-01 | 2016-08-01 | A method of removing polycyclic aromatic hydrocarbon |
| CN201810927213.7A Expired - Fee Related CN108927114B (en) | 2016-08-01 | 2016-08-01 | Method for efficiently adsorbing polycyclic aromatic hydrocarbon in spirulina |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810927445.2A Expired - Fee Related CN108940215B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in enrichment manner |
| CN201810927478.7A Expired - Fee Related CN108940216B (en) | 2016-08-01 | 2016-08-01 | Method for removing polycyclic aromatic hydrocarbon in spirulina |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810927213.7A Expired - Fee Related CN108927114B (en) | 2016-08-01 | 2016-08-01 | Method for efficiently adsorbing polycyclic aromatic hydrocarbon in spirulina |
Country Status (1)
| Country | Link |
|---|---|
| CN (4) | CN108940215B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109940029B (en) * | 2019-04-18 | 2020-06-30 | 重庆大学 | Method for degrading polycyclic aromatic hydrocarbon in waste incineration fly ash by catalyzing subcritical water oxidation |
| CN110586053B (en) * | 2019-09-24 | 2022-06-03 | 山西医科大学 | Solid phase extraction polycyclic aromatic hydrocarbon adsorbent and preparation method thereof |
| CN114433034B (en) * | 2020-11-02 | 2024-05-07 | 中国石油化工股份有限公司 | Super-crosslinked polymer modified magnetic nanoparticle and preparation method and application thereof |
| CN114130374B (en) * | 2021-11-04 | 2023-06-23 | 华南理工大学 | Application of magnetic carboxylated covalent organic framework material as magnetic solid-phase extraction adsorbent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706328A (en) * | 2014-01-17 | 2014-04-09 | 湖南大学 | Nitrogen hybridized magnetic ordered mesoporous carbon adsorbent, and preparation method and application thereof |
| CN104492494A (en) * | 2014-11-26 | 2015-04-08 | 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 |
Family Cites Families (8)
| 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 |
| EP2526121A4 (en) * | 2010-01-19 | 2013-11-13 | Organoclick Ab | Heterogeneous thiol-ene click modifications of solid polysaccharide-based materials |
| CN102145279B (en) * | 2010-02-05 | 2012-11-21 | 华中科技大学 | Method for preparing lysozyme molecular imprinting nano particles with magnetic responsiveness and extremely high adsorption capacity |
| CN102608093B (en) * | 2011-01-20 | 2014-04-30 | 中国科学院生态环境研究中心 | Detection method of polycyclic aromatic hydrocarbons (PAHs) |
| CN103183832B (en) * | 2011-12-28 | 2015-11-18 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of 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 |
| CN104892869B (en) * | 2015-06-23 | 2017-12-15 | 嘉兴学院 | Magnetic polymeric ionic liquid for detecting Microcystin and its preparation method and application |
| CN104910339B (en) * | 2015-06-23 | 2017-06-06 | 嘉兴学院 | Magnetic molecularly imprinted poly ion liquid and its production and use for detecting Ractopamine |
-
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 CN201610621741.0A patent/CN106111070B/en not_active Expired - Fee Related
- 2016-08-01 CN CN201810927213.7A patent/CN108927114B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706328A (en) * | 2014-01-17 | 2014-04-09 | 湖南大学 | Nitrogen hybridized magnetic ordered mesoporous carbon adsorbent, and preparation method and application thereof |
| CN104492494A (en) * | 2014-11-26 | 2015-04-08 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 磁固相萃取-气相色谱/质谱联用法测定环境水中的邻苯二甲酸二丁酯和邻苯二甲酸二(2－乙基己基)酯;Shishu Huang et al.;《分析实验室》;20140531;第33卷(第5期);第547-549页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106111070A (en) | 2016-11-16 |
| CN108927114B (en) | 2020-10-30 |
| CN108940215B (en) | 2020-12-22 |
| CN108940216B (en) | 2020-12-08 |
| CN108940216A (en) | 2018-12-07 |
| CN108927114A (en) | 2018-12-04 |
| CN108940215A (en) | 2018-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106111070B (en) | A method of removing polycyclic aromatic hydrocarbon | |
| Sun et al. | Adsorptive removal of dye and antibiotic from water with functionalized zirconium-based metal organic framework and graphene oxide composite nanomaterial Uio-66-(OH) 2/GO | |
| Yönten et al. | A thermodynamic and kinetic approach to adsorption of methyl orange from aqueous solution using a low cost activated carbon prepared from Vitis vinifera L. | |
| CN106732385B (en) | Composite magnetic hybrid material Fe3O4/ MOFs and its preparation method and application | |
| CN103105386B (en) | Method for detecting malachite green in water body and aquatic products | |
| CN106582543B (en) | Chiral MOF- magnetic graphenes functional material and its preparation method and application | |
| CN109499529A (en) | A kind of magnetic porous carbon material of N doping and its preparation method and application | |
| Subhan et al. | Effective adsorptive performance of Fe 3 O 4@ SiO 2 core shell spheres for methylene blue: Kinetics, isotherm and mechanism | |
| Chen et al. | Ultrastable nitrogen-doped carbon nanotube encapsulated cobalt nanoparticles for magnetic solid-phase extraction of okadaic acid from aquatic samples | |
| Banaei et al. | Synthesis and characterization of new modified silica coated magnetite nanoparticles with bisaldehyde as selective adsorbents of Ag (I) from aqueous samples | |
| CN111871400B (en) | Preparation method and application of guanidine salt ionic liquid modified magnetic solid phase extraction adsorbent | |
| Cheng et al. | Vortex-assisted magnetic dispersive solid-phase microextraction for rapid screening and recognition of dicofol residues in tea products | |
| Song et al. | Morphology-maintaining synthesis of copper hydroxy phosphate@ metal–organic framework composite for extraction and determination of trace mercury in rice | |
| CN105688869A (en) | Preparation method and application of magnetic metal - organic nanotube material | |
| Li et al. | Polyethyleneimine-functionalized Fe 3 O 4/attapulgite particles for hydrophilic interaction-based magnetic dispersive solid-phase extraction of fluoroquinolones in chicken muscle | |
| CN109400889A (en) | A kind of Metal Porous-Organic material of magnetic modification and its preparation and application | |
| CN106699952A (en) | Method for preparing phenylboronic-acid-based magnetic imprinted polymer | |
| Liang et al. | Using recycled coffee grounds for the synthesis of ZIF-8@ BC to remove Congo red in water | |
| Mehraban et al. | Trace amount determination of Cd (II), Pb (II) and Ni (II) ions in agricultural and seafood samples after magnetic solid phase extraction by MIL-101 (Cr)/phenylthiosemicarbazide-functionalized magnetite nanoparticle composite | |
| CN108586660A (en) | The preparation method of TNT magnetic molecularly imprinted polymer microballoons | |
| CN105833838B (en) | A kind of magnetic Nano material and its preparation method and application | |
| Liu et al. | Simple synthesis of magnetic porous organic cages for adsorption of triphenylmethane dyes in aquatic products | |
| CN112958041A (en) | Core-shell structure nano composite resin, preparation method and application in electroplating wastewater treatment | |
| Zhu et al. | One-step preparation of coal-based magnetic activated carbon with hierarchically porous structure and easy magnetic separation capability for adsorption applications | |
| CN106905696B (en) | A kind of synthetic method of magnetism phosphorescence Microcystin imprinted material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180911 |