CN109745962A - A kind of mixed modified organic montmorillonite and its synthesis method and application - Google Patents
A kind of mixed modified organic montmorillonite and its synthesis method and application Download PDFInfo
- Publication number
- CN109745962A CN109745962A CN201910197900.2A CN201910197900A CN109745962A CN 109745962 A CN109745962 A CN 109745962A CN 201910197900 A CN201910197900 A CN 201910197900A CN 109745962 A CN109745962 A CN 109745962A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- modified
- poly
- solution
- mixed
- 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.)
- Pending
Links
- 229910017059 organic montmorillonite Inorganic materials 0.000 title claims abstract 16
- 238000001308 synthesis method Methods 0.000 title 1
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 130
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 97
- -1 poly-4-vinyl pyridine styrene-modified montmorillonite Chemical class 0.000 claims abstract description 64
- 238000006731 degradation reaction Methods 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 36
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- CIPXQVPZUWMSQE-UHFFFAOYSA-N 4-ethenylpyridine;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=NC=C1 CIPXQVPZUWMSQE-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000003617 indole-3-acetic acid Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 47
- 239000013049 sediment Substances 0.000 claims description 46
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052753 mercury Inorganic materials 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000005341 cation exchange Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- KCBLLBVZKWDPJD-UHFFFAOYSA-N 1-bromo-N,N-dimethylheptadecan-1-amine Chemical compound BrC(N(C)C)CCCCCCCCCCCCCCCC KCBLLBVZKWDPJD-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 49
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006115 defluorination reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 231100001239 persistent pollutant Toxicity 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 51
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XQQSWXUDAPLMKD-UHFFFAOYSA-N N,N-dimethylheptadecan-1-amine hydrobromide Chemical compound Br.CCCCCCCCCCCCCCCCCN(C)C XQQSWXUDAPLMKD-UHFFFAOYSA-N 0.000 description 19
- 238000005119 centrifugation Methods 0.000 description 18
- 239000002689 soil Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000031709 bromination Effects 0.000 description 8
- 238000005893 bromination reaction Methods 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
- 238000004255 ion exchange chromatography Methods 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000005291 magnetic effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000012552 review Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920006926 PFC Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005183 environmental health Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 2
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-M 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-M 0.000 description 1
- QWLULCKKOHDCIE-UHFFFAOYSA-N 2,3-dimethyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=C[N+]([O-])=C1C QWLULCKKOHDCIE-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- 208000036864 Attention deficit/hyperactivity disease Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZOFMEZKHZDNWFN-UHFFFAOYSA-N acetic acid methane Chemical compound C.CC(O)=O ZOFMEZKHZDNWFN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 208000015802 attention deficit-hyperactivity disease Diseases 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004578 fetal growth Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 208000013403 hyperactivity Diseases 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RNFHYRYYUYDKTR-UHFFFAOYSA-N pyridine;styrene Chemical compound C1=CC=NC=C1.C=CC1=CC=CC=C1 RNFHYRYYUYDKTR-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明公开了一种混合改性有机蒙脱土及其合成方法以及在高效降解全氟化合物中的应用，属于持久性污染物降解领域。本发明首先使用聚‑4‑乙烯基吡啶苯乙烯对蒙脱土进行有机改性，再使用十六烷基三甲基溴化氨对聚‑4‑乙烯基吡啶苯乙烯改性蒙脱土进行有机改性，得到混合改性有机蒙脱土；该混合改性有机蒙脱土具有增加对水合电子前驱物吲哚乙酸的吸附和保护水合电子的优点，能够实现对PFOA的快速降解和脱氟，且本发明降解全氟化合物的方法不受溶液pH、NO3 ‑、SO4 2‑以及溶解氧的影响，具有较高的应用价值。
The invention discloses a mixed modified organic montmorillonite, a method for synthesizing the same, and an application in the efficient degradation of perfluorinated compounds, belonging to the field of persistent pollutant degradation. The present invention firstly uses poly-4-vinyl pyridine styrene to organically modify montmorillonite, and then uses cetyltrimethyl ammonium bromide to conduct poly-4-vinyl pyridine styrene-modified montmorillonite. Organic modification to obtain a mixed modified organic montmorillonite; the mixed modified organic montmorillonite has the advantages of increasing the adsorption of the hydrated electron precursor indoleacetic acid and protecting the hydrated electrons, and can achieve rapid degradation and defluorination of PFOA , and the method for degrading perfluorinated compounds of the present invention is not affected by solution pH, NO 3 ‑ , SO 4 2 ‑ and dissolved oxygen, and has high application value.
Description
Technical field
The invention belongs to persistent pollutant degradation fields, more specifically to a kind of mixed and modified organo montmorillonite
And its synthetic method and application.
Background technique
Since last century the fifties, perfluorochemical is extensive due to fabulous physics and chemical stability
Applied to industrial different field, as coating, fire proofing material, Macroscopic single crystal and polishing agent (Renner, R.,
Evidence of toxic effects and environmental impacts has sent researchers
scrambling to obtain more data.Environmental science&technology 2001,35,(7),
154A-160A.Schultz,M.M.；Barofsky,D.F.；Field,J.A.,Fluorinated alkyl
surfactants.Environmental Engineering Science 2003,20,(5),487-501.Giesy,J.P.；
Kannan,K.,Perfluorochemical surfactants in the environment.Environmental
science&technology 2002,36,(7),146A-152A).In a series of perfluorochemical, perfluoro caprylic acid be by
The highest perfluorochemical of content, recent years receive significant attention (Rahman, M.F. in the environment detected；Peldszus,
S.；Anderson,W.B.,Behaviour and fate of perfluoroalkyl and polyfluoroalkyl
substances(PFASs)in drinking water treatment:a review.Water research 2014,50,
318-40).Scientific research before confirms that perfluoro caprylic acid can cause the growth and development of embryo slow.In addition to this, it also grinds
Study carefully discovery for 5 to 18 years old youngsters and childrens, the hyperactivity of perfluoro caprylic acid concentration in blood and children, which are presented, to be positively correlated
Relationship.(Koustas,E.；Lam,J.；Sutton,P.；Johnson,P.I.；Atchley,D.S.；Sen,S.；Robinson,
K.A.；Axelrad,D.A.；Woodruff,T.J.,The Navigation Guide-evidence-based medicine
meets environmental health:systematic review of nonhuman evidence for PFOA
effects on fetal growth.Environmental health perspectives 2014,122,(10),1015-
27.Stein,C.R.；Savitz,D.A.,Serum Perfluorinated Compound Concentration and
Attention Deficit/Hyperactivity Disorder in Children 5-18Years of
Age.Environmental health perspectives 2011,119,(10),1466-1471)。
PFOA is the compound that hydrogen atom all in a kind of sad carbochain is all replaced by fluorine atoms.Since fluorine atom is strong
Electronegativity, carbon-fluorine bond is considered as strongest chemical bond (carbon-fluorine bond bond energy 485kJ/mol), and there are also very strong anti-oxidant
Ability, this shows compared to oxidative degradation technology, and PFOA is easier to be reduced degradation.(Rahman,M.F.；Peldszus,S.；
Anderson,W.B.,Behaviour and fate of perfluoroalkyl and polyfluoroalkyl
substances(PFASs)in drinking water treatment:a review.Water research 2014,50,
318-40.Arvaniti,O.S.；Stasinakis,A.S.,Review on the occurrence,fate and
removal of perfluorinated compounds during wastewater treatment.The Science
of the total environment 2015,524-525,81-92.Park,H.；Vecitis,C.D.；Cheng,J.；
Choi,W.；Mader,B.T.；Hoffmann,M.R.,Reductive Defluorination of Aqueous
Perfluorinated Alkyl Surfactants:Effects of Ionic Headgroup and Chain
Length.Journal of Physical Chemistry A 2009,113,(4),690-696).In a recent study,
The methods of many reduction PFOA are reported, including direct ultraviolet illumination, ultraviolet/sulphite, ultraviolet/potassium iodide, ultraviolet/light are urged
The technical methods such as agent (Lyu, X.J.；Li,W.W.；Lam,P.K.；Yu,H.Q.,Insights into
perfluorooctane sulfonate photodegradation in a catalyst-free aqueous
solution.Scientific reports 2015,5,9353.Gu,Y.；Dong,W.；Luo,C.；Liu,T.,Efficient
Reductive Decomposition of Perfluorooctanesulfonate in a High Photon Flux UV/
Sulfite System.Environmental science&technology 2016,50,(19),10554-10561.Qu,
Y.；Zhang,C.；Li,F.；Chen,J.；Zhou,Q.,Photo-reductive defluorination of
perfluorooctanoic acid in water.Water research 2010,44,(9),2939-47.Lin,H.；
Niu,J.；Xu,J.；Huang,H.；Li,D.；Yue,Z.；Feng,C.,Highly efficient and mild
electrochemical mineralization of long-chain perfluorocarboxylic acids(C9-
C10)by Ti/SnO2-Sb-Ce,Ti/SnO2-Sb/Ce-PbO2,and Ti/BDD electrodes.Environmental
science&technology 2013,47,(22),13039-46.Li,X.；Zhang,P.；Jin,L.；Shao,T.；Li,Z.；
Cao,J.,Efficient photocatalytic decomposition of perfluorooctanoic acid by
indium oxide and its mechanism.Environmental science&technology 2012,46,(10),
5528-34.Tang,H.；Xiang,Q.；Lei,M.；Yan,J.；Zhu,L.；Zou,J.,Efficient degradation of
perfluorooctanoic acid by UV–Fenton process.Chemical Engineering Journal
2012,184,156-162.Liu,Y.；Chen,S.；Quan,X.；Yu,H.；Zhao,H.；Zhang,Y.,Efficient
Mineralization of Perfluorooctanoate by Electro-Fenton with H2O2Electro-
generated on Hierarchically Porous Carbon.Environmental science&technology
2015,49,(22),13528-33).In these methods, reduction activation species such as aqueous electron, carbon dioxide anion from
Main function is played by base and light induced electron.In addition to this, these researchs also indicate that free compared to carbon dioxide anion
Base and light induced electron, the strong reducing power of aqueous electron can be by the complete defluorinate of PFOA, therefore this method is with higher answers
Use prospect.But aqueous electron needs more harsh reaction condition (such as anaerobic environment, height during deoxidization, degradation PFOA
PH), harsh reaction condition increases the not applicability of this method in practical applications.Therefore, a kind of low energy consumption, degradation
High-efficient, the strong method of applicability is urgently developed.
It is found through retrieval, Chinese Patent Application No. 201510981853.2, data of publication of application is the special of on May 4th, 2016
Sharp application documents disclose a kind of method of efficient degradation perfluorochemical, use 254nm ultraviolet light heteroauxin (IAA)
Solution generates aqueous electron, and the deoxidization, degradation PFCs under aerobic condition, by being added, cetyl trimethylammonium bromide is organic to be changed
The montmorillonite of property provides reaction microcell, substantially increases degradation and defluorination effect of the aqueous electron to PFCs, and this method
It is not influenced by pH value of solution and dissolved oxygen, substantially overcomes the defect of existing aqueous electron deoxidization, degradation PFCs method.The invention
Principle be use cetyl trimethylammonium bromide ion (HDTMA+Ion) balance montmorillonite interlayer negative electrical charge, had
Machine modified montmorillonoid, and utilize HDTMA+Longer C chain, make organo montmorillonite have hydrophobicity, to increase it to perfluor
The absorption of compound and heteroauxin, under ultraviolet lighting, the heteroauxin for being adsorbed onto interlayer occurs photoionization and generates water
Electronics is closed, these aqueous electrons can degrade perfluorochemical by way of restoring defluorinate.But the technology is to perfluor chemical combination
The degradation efficiency of object is limited, to improve degradation efficiency, needs to be further improved organic modification montmonrillonite.
Summary of the invention
1. solving the problems, such as
For existing aqueous electron deoxidization, degradation perfluorochemical technology there are severe reaction conditions, applicability it is poor,
Aqueous electron utilization rate and degradation efficiency need the problem of being further increased, and the present invention provides a kind of mixed and modified organic illiteracy is de-
Soil and its synthetic method and application；The present invention is first organically-modified to montmorillonite progress using poly- 4-vinylpridine styrene, then
It is organically-modified to poly- 4-vinylpridine phenylethene modified montmorillonite progress using cetyl trimethyl ammonia bromide, it is mixed
Close modified organo montmorillonite.Using the mixed and modified organo montmorillonite as catalytic media, in the aqueous solution containing heteroauxin,
Degrade PFOA under ultraviolet lighting.The mixed and modified organo montmorillonite has the absorption increased to aqueous electron predecessor heteroauxin
The advantages of with protection aqueous electron, so as to realize fast degradation and the defluorinate under aerobic and acid condition to PFOA.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of method synthesizing mixed and modified organo montmorillonite of the invention, comprising the following steps:
S1, using poly- 4-vinylpridine styrene (PVPcoS) to montmorillonite (MMT) carry out it is organically-modified, obtain poly-
The phenylethene modified montmorillonite of 4-vinylpridine (PVPcoS-MMT)；
S2, using cetyl trimethyl ammonia bromide (HDTMA) to poly- 4-vinylpridine benzene second obtained in step S1
The progress of alkene modified montmorillonoid is organically-modified again, obtains mixed and modified organo montmorillonite (MOM-MMT).
Preferably, the total amount of the poly- 4-vinylpridine styrene in the step S1 is exchanged with the cation of montmorillonite
(CEC) total amount is consistent.
Preferably, the total amount of the cetyl trimethyl ammonia bromide in the step S2 is less than the cation exchange of montmorillonite
Total amount.
Preferably, the total amount of the cetyl trimethyl ammonia bromide in the step S2 is that the cation exchange of montmorillonite is total
0.6~0.8 times of amount.
Preferably, organically-modified specific steps are carried out to montmorillonite in the step S1 are as follows:
(1) na montmorillonite is distributed in water, obtains montmorillonite dispersion solution；
(2) the poly- 4-vinylpridine styrene solution of acidification is added into the montmorillonite of step (1) dispersion solution, stirs
It mixes；
(3) it is centrifuged after stirring in step (2), discards supernatant liquid, obtain sediment；
(4) sediment obtained in step (3) is washed with water, the phenylethene modified montmorillonite of poly- 4-vinylpridine is obtained.
Preferably, the phenylethene modified montmorillonite of poly- 4-vinylpridine is carried out in the step S2 organically-modified again
Specific steps are as follows:
(1) the phenylethene modified montmorillonite of poly- 4-vinylpridine is distributed in water, obtains poly- 4-vinylpridine benzene
Ethylene modified montmorillonite disperses solution；
(2) cetyl three is added into the phenylethene modified montmorillonite dispersion solution of the poly- 4-vinylpridine of step (1)
Methyl bromide ammonium salt solution, stirring；
(3) it is centrifuged after stirring in step (2), discards supernatant liquid, obtain sediment；
(4) sediment obtained in step (3) is washed with water, mixed and modified organo montmorillonite is obtained.
Preferably, carrying out jitter time in organically-modified specific steps (1) to montmorillonite in the step S1 is 8 small
When.
Preferably, montmorillonite cleaned in organically-modified specific steps (4) with deionized water in the step S1
Sediment 10 times.
A kind of mixed and modified organo montmorillonite of the invention, using the method for the above-mentioned mixed and modified organo montmorillonite of synthesis
Synthesis obtains.
A kind of method using mixed and modified organo montmorillonite efficient degradation perfluorochemical of the invention, including following step
It is rapid:
(i) heteroauxin solution and perfluorochemical solution are uniformly mixed；
(ii) above-mentioned mixed and modified organo montmorillonite is distributed in the mixed solution of step (i), obtains reaction solution；
(iii) light reaction is carried out with degrading perfluorinated compound to reaction solution obtained in step (ii) using mercury lamp.
Preferably, the step (ii) further includes adjusting the pH value of reaction solution to 4.0~10.0.
Preferably, the specific steps of the step (iii) are as follows: stir reaction solution obtained in step (ii) 30 minutes
After be transferred in crystal reaction tube, under aerobic environment, mercury lamp is immersed into reaction solution and carries out degradation reaction；Wherein, always
Reaction solution volume is 300mL, and at 25 ± 2 DEG C, mercury lamp is 36W low pressure mercury lamp for reaction temperature control, and the reaction time is 14 hours.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) a kind of method for synthesizing mixed and modified organo montmorillonite of the invention, including poly- 4- vinylpyridine is used first
Pyridine styrene is organically-modified to montmorillonite progress, reuses cetyl trimethyl ammonia bromide to poly- 4-vinylpridine benzene second
The progress of alkene modified montmorillonoid is organically-modified to obtain mixed and modified organo montmorillonite, has surprisingly found that mixed and modified organo montmorillonite energy
The adsorption efficiency to heteroauxin molecule is enough greatly increased, more aqueous electron precursors is promoted to generate in interlayer, thus
The utilization rate in reaction process to aqueous electron is improved, promotes the degradation of PFOA, therefore use poly- 4-vinylpridine styrene
Montmorillonite is carried out organically-modified for the first time；
(2) a kind of mixed and modified organo montmorillonite of the invention successively passes through poly- 4-vinylpridine styrene, 16
The modification of alkyl trimethyl ammonia bromide obtains, which is adsorbed with poly- 4-vinylpridine benzene simultaneously
Ethylene and cetyl trimethyl ammonia bromide protect the photoproduction largely generated to be hydrated while increasing to heteroauxin absorption
Electronics is not quenched by oxygen and proton, so that degradation reaction be allow to occur under aerobic and acid condition, and passes through control
The amount of modified poly- 4-vinylpridine styrene used, cetyl trimethyl ammonia bromide twice, makes mixed and modified organic illiteracy
De- native degradation with higher to perfluorochemical and defluorinate efficiency；
(3) a kind of method using mixed and modified organo montmorillonite efficient degradation perfluorochemical of the invention, in use
For the mixed and modified organo montmorillonite stated as catalytic media, the presence of the mixed and modified organo montmorillonite plays a micro- reaction
Efficient degradation PFOA is realized in the effect of device；
(4) montmorillonite and heteroauxin used in the present invention are all the substances that nature is widely present, will not be to environment
It pollutes, the poly- 4-vinylpridine styrene of used organic modifiers and cetyl trimethyl ammonia bromide can be by
It fixes well, will not can be discharged into environment and cause secondary pollution, realize green environment close friend.
Detailed description of the invention
Fig. 1 is the schematic diagram that PFOA degrades in mixed and modified montmorillonite in the present invention；
Fig. 2 is the schematic diagram of PFOA degradation mechanism in the present invention；
Fig. 3 a is organic modification montmonrillonites different in the present invention to the Adsorption thermodynamics curve graph of IAA；
Fig. 3 b is organic modification montmonrillonites different in the present invention to the Adsorption thermodynamics curve graph of PFOA；
Fig. 4 is organic modification montmonrillonites different in the present invention to the degradation figure of PFOA；
Fig. 5 a and 5b are the dynamic curve diagram that aqueous electron degrades to PFOA under different atmosphere in the present invention；
Fig. 5 c and 5d are the dynamic curve diagram that aqueous electron degrades to PFOA under condition of different pH in the present invention；
Fig. 6 is the intermediate product dynamic curve diagram that aqueous electron degrades to PFOA in the present invention；
Fig. 7 is the dynamic curve diagram that aqueous electron degrades to PFOA in the presence of different anions in the present invention；
Fig. 8 is the electron paramagnetic resonance spectrum figure of aqueous electron in different montmorillonite systems in the present invention.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Hereafter to the detailed description of exemplary embodiment of the present invention with reference to attached drawing, although these exemplary embodiment quilts
Sufficiently describe in detail so that those skilled in the art can implement the present invention, it is to be understood that can realize other embodiments and
Can without departing from the spirit and scope of the present invention to the present invention various changes can be made.Hereafter to the embodiment of the present invention
More detailed description is not limited to required the scope of the present invention, and just to be illustrated and do not limit pair
The description of the features of the present invention and feature to propose to execute best mode of the invention, and is sufficient to make those skilled in the art
It can implement the present invention.Therefore, the scope of the invention is only defined by the appended claims.
A kind of method synthesizing mixed and modified organo montmorillonite of the invention, comprising the following steps:
S1, na montmorillonite is distributed in water, stirring obtains montmorillonite dispersion solution for 8 hours；Disperse again to montmorillonite molten
The poly- 4-vinylpridine styrene that acidification is added in liquid carries out organically-modified, the poly- 4-vinylpridine of addition to montmorillonite
The total amount of styrene is consistent with the cation exchange total amount of montmorillonite, stirs 24 hours, and centrifugation discards supernatant liquid, is precipitated
Object, and clean sediment 10 times with deionized water water and obtain the phenylethene modified montmorillonite of poly- 4-vinylpridine；
S2, the phenylethene modified montmorillonite of poly- 4-vinylpridine will be obtained in step S1 be distributed in water, stir 1 hour；
The cetyl trimethyl ammonia bromide for being less than montmorillonite cation exchange total amount is stirring evenly and then adding into poly- 4-vinylpridine
Phenylethene modified montmorillonite progress is organically-modified again, and the total amount for the cetyl trimethyl ammonia bromide being usually added into is montmorillonite
0.6~0.8 times of cation exchange total amount, is stirred 24 hours, and centrifugation discards supernatant liquid, obtains sediment, and use deionization
Water water cleans sediment 10 times and obtains mixed and modified organo montmorillonite.
It is worth noting that the poly- 4-vinylpridine styrene that acidification is added in step S1 is poly- in order to be easier to carry out
4-vinylpridine is phenylethene modified, carries out organically-modified to montmorillonite using poly- 4-vinylpridine styrene so that covering de-
Soil can greatly increase the adsorption efficiency to heteroauxin molecule, and more aqueous electron precursors is promoted to generate in interlayer,
Promote the degradation of PFOA.
It further illustrates, a kind of mixed and modified organo montmorillonite of the invention successively uses poly- 4-vinylpridine
Styrene, cetyl trimethyl ammonia bromide carry out modification twice and obtain, the total amount of poly- 4-vinylpridine styrene with illiteracy
The cation exchange total amount of de- soil is consistent, and the total amount of cetyl trimethyl ammonia bromide is the cation exchange total amount of montmorillonite
0.6~0.8 times, by controlling the amount of poly- 4-vinylpridine styrene, cetyl trimethyl ammonia bromide and montmorillonite, make
It is with higher to perfluorochemical while heteroauxin adsorption capacity with higher to obtain mixed and modified organo montmorillonite
Degradation and defluorinate efficiency.
A kind of method using mixed and modified organo montmorillonite efficient degradation perfluorochemical of the invention, including following step
It is rapid:
(i) heteroauxin solution and perfluorochemical solution are uniformly mixed；
(ii) above-mentioned mixed and modified organo montmorillonite is distributed in the mixed solution of step (i), uses NaOH or HCl
The pH value of reaction solution is adjusted to 4.0~10.0, obtains reaction solution；
(iii) reaction solution obtained in step (ii) is stirred 30 minutes using magnetic agitation, it will be anti-after stirring
It answers solution to be transferred in crystal reaction tube, under aerobic environment, mercury lamp is immersed into reaction solution and carries out degradation reaction；Its
In, overall reaction liquid product is 300mL, and at 25 ± 2 DEG C, mercury lamp is 36W low pressure mercury lamp for reaction temperature control, and the reaction time is 14 small
When.
The present invention uses the principle of mixed and modified organo montmorillonite efficient degradation perfluorochemical are as follows: montmorillonite mineral are one
The mineral material of kind layer structure, interlayer have negative electrical charge, can be modified by the organic modifiers with positive charge.It is cationic
Polymer (poly- 4-vinylpridine styrene) modified organo montmorillonite is increased to aqueous electron predecessor heteroauxin
Absorption, aqueous electron can be protected sudden not by oxygen and proton by the modified montmorillonite of cetyl trimethyl ammonia bromide
It goes out.Therefore, organically-modified by using poly- 4-vinylpridine styrene to carry out montmorillonite first, reuse cetyl
Trimethyl ammonia bromide carries out organically-modified obtained mixed and modified organic illiteracy to the phenylethene modified montmorillonite of poly- 4-vinylpridine
De- soil, can not only increase adsorb to aqueous electron predecessor heteroauxin in this way, improve aqueous electron utilization rate, and can
Protect aqueous electron, do not quenched by oxygen and proton, thus realize under aerobic and acid condition to the fast degradation of PFOA and
Defluorinate.
Embodiment 1
The present embodiment measures suction of the different organic modification montmonrillonites to perfluorooctane carboxylic acid (PFOA) and heteroauxin (IAA)
Attached rate, the steps include:
(1) 200g montmorillonite (being purchased from Zhejiang Feng Hong montmorillonite Chemical Co., Ltd.) is dispersed in 4L water, is added
0.4mol solid NaCl is saturated 8h, and centrifugation discards supernatant liquid, obtains sediment；Sediment is redispersed in 4L water, so weight
It operates 6 times again.Sediment is cleaned with deionized water, is washed till with AgNO3Solution detection is generated without precipitating.Freeze-drying is satisfied
The Na of sum+Montmorillonite；
(2) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
Total amount of electric charge is added in de- soil solution and exchanges the consistent poly- 4-vinylpridine benzene second of total amount with the cation of montmorillonite in solution
Alkene (is dissolved in 5mol/L H2SO4) aqueous solution 50mL, it stirs 24 hours, centrifugation obtains sediment, washes with water sediment, obtains
Poly- 4-vinylpridine styrene montmorillonite (PVPcoS-MMT)；
(3) the phenylethene modified montmorillonite of poly- 4-vinylpridine is dispersed in water, is stirred 1 hour.It stirs evenly
Afterwards, 0.2CEC, 0.4CEC, 0.6CEC, 0.8CEC are separately added into scattered poly- 4-vinylpridine styrene montmorillonite
The cetyl trimethyl bromination ammonia solution of amount stirs 24 hours, and centrifugation obtains sediment, washes with water sediment, is mixed
It closes modified organo montmorillonite (0.2MOM-MMT, 0.4MOM-MMT, 0.6MOM-MMT, 0.8MOM-MMT)；
(4) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
The cetyl trimethyl bromination ammonia spirit of 1CEC is added in de- soil solution, stirs 24 hours, centrifugation obtains sediment, spends
Ionized water water cleans sediment, obtains cetyl trimethyl ammonia bromide modified montmorillonoid (HDTMA-MMT)；
(5) prepare PFOA aqueous solution each 10mL of the initial concentration from 0 to 1000mg/L, be separately added into 22mg Na+Montmorillonite
Or organic modification montmonrillonite, 10h is shaken at room temperature, and centrifuging and taking supernatant measures the concentration of PFOA, quasi- using langmuir model
Close the adsorption isotherm to PFOA, model Qe=(KL×Cmax×Ce)/(1+KL×Ce), PFOA is obtained in different montmorillonites
Maximal absorptive capacity be respectively Qe(mmol/kg)=8.199, PFOA is in HDTMA+Maximal absorptive capacity Q in montmorillonitee(mmol/
Kg)=277.312.Similarly, prepare IAA aqueous solution each 10mL of the initial concentration from 17.52 to 525.6mg/L, be separately added into
22mg Na+Montmorillonite or organic modification montmonrillonite shake 4h at room temperature, and centrifuging and taking supernatant measures the concentration of IAA, use
Adsorption isotherm of the langmuir models fitting to IAA, model Qe=(KL×Cmax×Ce)/(1+KL×Ce), it obtains IAA and exists
Maximal absorptive capacity in different montmorillonites is respectively Qe(mmol/kg)=156, IAA is in HDTMA+Maximal absorptive capacity in montmorillonite
Qe(mmol/kg)=277.
It follows that: the absorption to IAA is greatly facilitated in organic modification montmonrillonite, as mixed and modified cover takes off
The increase of poly- 4-vinylpridine styrene-content in soil, modified montmorillonoid increase IAA adsorbance, as shown in Figure 3a.It is surprised
Discovery compared with HDTMA- montmorillonite, mixed and modified montmorillonite reduces PFOA adsorbance, as shown in Figure 3b.
Embodiment 2
A kind of method of efficient degradation perfluorochemical of the present embodiment, the steps include:
(1) 200g montmorillonite (being purchased from Zhejiang Feng Hong montmorillonite Chemical Co., Ltd.) is dispersed in 4L water, is added
0.4mol solid NaCl is saturated 8h, and centrifugation discards supernatant liquid, obtains sediment；Sediment is redispersed in 4L water, so weight
It operates 6 times again.Sediment is cleaned with deionized water, is washed till with AgNO3Solution detection is generated without precipitating.Freeze-drying is satisfied
The Na of sum+Montmorillonite；
(2) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
Total amount of electric charge is added in de- soil solution and exchanges the consistent poly- 4-vinylpridine benzene second of total amount with the cation of montmorillonite in solution
Alkene (is dissolved in 5mol/L H2SO4) aqueous solution 50mL, it stirs 24 hours, centrifugation obtains sediment, washes with water sediment, obtains
Poly- 4-vinylpridine styrene montmorillonite (PVPcoS-MMT)；
(3) the phenylethene modified montmorillonite of poly- 4-vinylpridine is dispersed in water, is stirred 1 hour.It stirs evenly
Afterwards, 0.2CEC, 0.4CEC, 0.6CEC, 0.8CEC are separately added into scattered poly- 4-vinylpridine styrene montmorillonite
The cetyl trimethyl bromination ammonia solution of amount stirs 24 hours, and centrifugation obtains sediment, washes with water sediment, is mixed
It closes modified organo montmorillonite (0.2MOM-MMT, 0.4MOM-MMT, 0.6MOM-MMT, 0.8MOM-MMT)；
(4) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
The cetyl trimethyl bromination ammonia spirit of 1CEC is added in de- soil solution, stirs 24 hours, centrifugation obtains sediment, spends
Ionized water water cleans sediment, obtains cetyl trimethyl ammonia bromide modified montmorillonoid (HDTMA-MMT)；
(5) before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution (are chosen into PFOA as perfluorochemical first
Representative substances) be uniformly mixed.Above-mentioned different montmorillonites are distributed in the mixed solution of IAA and PFOA, obtain IAA,
PFOA and the content of montmorillonite are respectively the reaction solution of 2mM, 10mg/L and 2.2g/L.Then the NaOH and HCl of 0.1mM are used
The pH to 7.0 for adjusting reaction solution stirs reaction solution 30 minutes using magnetic agitation, turns reaction solution after stirring
It moves to and is equipped in the light reaction instrument of 500W high-pressure sodium lamp, turn on light and carry out degradation reaction, total reaction volume 30mL, reaction temperature
At 25 ± 2 DEG C, the reaction time is 6 hours for control.Sampling and testing after 6 hours, sample are divided into two parts, the second of a 2 times of volumes
Residue PFOA content is measured with high performance liquid chromatography (HPLC) after nitrile extraction, with ion chromatography (IC) measurement life after another filtering
At F ion content, the degradation rate and defluorinate rate of PFOA are calculated with this, specific degradation and defluorinate curve are as shown in Figure 4.
From this it can be concluded that the deoxidization, degradation of PFOA is greatly promoted in the case where being added to organo montmorillonite
, wherein the mixed and modified organo montmorillonite of 0.6MOM-MMT shows highest defluorinate and degradation efficiency.
Embodiment 3
A kind of method of efficient degradation perfluorochemical of the present embodiment, the steps include:
(1) 200g montmorillonite (being purchased from Zhejiang Feng Hong montmorillonite Chemical Co., Ltd.) is dispersed in 4L water, is added
0.4mol solid NaCl is saturated 8h, and centrifugation discards supernatant liquid, obtains sediment；Sediment is redispersed in 4L water, so weight
It operates 6 times again.Sediment is cleaned with deionized water, is washed till with AgNO3Solution detection is generated without precipitating.Freeze-drying is satisfied
The Na of sum+Montmorillonite；
(2) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
Total amount of electric charge is added in de- soil solution and exchanges the consistent poly- 4-vinylpridine benzene second of total amount with the cation of montmorillonite in solution
Alkene (is dissolved in 5mol/L H2SO4) aqueous solution 50mL, it stirs 24 hours, centrifugation obtains sediment, washes with water sediment, obtains
Poly- 4-vinylpridine styrene montmorillonite (PVPcoS-MMT)；
(3) the phenylethene modified montmorillonite of poly- 4-vinylpridine is dispersed in water, is stirred 1 hour.It stirs evenly
Afterwards, 0.2CEC, 0.4CEC, 0.6CEC, 0.8CEC are separately added into scattered poly- 4-vinylpridine styrene montmorillonite
The cetyl trimethyl bromination ammonia solution of amount stirs 24 hours, and centrifugation obtains sediment, washes with water sediment, is mixed
It closes modified organo montmorillonite (0.2MOM-MMT, 0.4MOM-MMT, 0.6MOM-MMT, 0.8MOM-MMT)；
(4) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
The cetyl trimethyl bromination ammonia spirit of 1CEC is added in de- soil solution, stirs 24 hours, centrifugation obtains sediment, spends
Ionized water water cleans sediment, obtains cetyl trimethyl ammonia bromide modified montmorillonoid (HDTMA-MMT)；
(5) the case where aqueous electron degrades to PFOA under different atmosphere is investigated:
Before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution are uniformly mixed first, then by 0.6MOM-MMT points
It is scattered in the mixed solution of IAA and PFOA, the content for obtaining IAA, PFOA and montmorillonite is respectively 2mM, 10mg/L and 2.2g/L
Reaction solution.Then the pH to 7.0 that reaction solution is adjusted using the NaOH and HCl of 0.1mM, it is molten to reaction using magnetic agitation
Liquid stirs 30 minutes, and reaction solution is transferred in crystal reaction tube after stirring, and overall reaction liquid product is 300ml, by one
Small cup 36W mercury lamp is immersed into reaction solution, is turned on light and is carried out degradation reaction.Reaction temperature control is at 25 ± 2 DEG C, the reaction time 14
Hour.It is tested in the environment for exposing nitrogen, not being aerated, exposing air respectively, aeration speed 4L/min.Sample time sets respectively
It is set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h, 14h.Sample is divided into two parts, the second of a 2 times of volumes
Residue PFOA content is measured with high performance liquid chromatography (HPLC) after nitrile extraction, with ion chromatography (IC) measurement life after another filtering
At F ion content, the degradation rate and defluorinate rate of PFOA are calculated with this, specific degradation and defluorinate curve are as shown in figure 5a and 5b.
From this it can be concluded that defluorinate rate and degradation rate are basic in the case where exposing nitrogen and the experiment condition not being aerated
Constant, the experimental group degradation rate for exposing air improves, and defluorinate rate only has seldom reduction, therefore it can be concluded that mixed and modified illiteracy
De- soil has good closure, can protect aqueous electron and not quenched by oxygen, improve the utilization rate of aqueous electron.
Embodiment 4
The basic content of the present embodiment is with embodiment 3, the difference is that the efficient degradation perfluorochemical of the present embodiment
Step (5) in method is to investigate the case where aqueous electron degrades to PFOA under condition of different pH, concrete operation step are as follows:
Before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution are uniformly mixed first, then by 0.6MOM-MMT points
It is scattered in the mixed solution of IAA and PFOA, the content for obtaining IAA, PFOA and montmorillonite is respectively 2mM, 10mg/L and 2.2g/L
Reaction solution.Then the pH of reaction solution is adjusted respectively to 4.0,7.0,10.0 using the NaOH and HCl of 0.1mM.Use magnetic
Reaction solution is stirred in power stirring 30 minutes, reaction solution is transferred in crystal reaction tube after stirring, overall reaction liquid
Product is 300ml, and a 36W mercury lamp is immersed into reaction solution, turns on light and carries out degradation reaction.Reaction temperature is controlled 25 ± 2
DEG C, the reaction time is 14 hours.Sample time be respectively set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h,
14h.Sample is divided into two parts, and is contained after the acetonitrile extraction of a 2 times of volumes with high performance liquid chromatography (HPLC) measurement residue PFOA
Amount, the F ion content generated after another filtering with ion chromatography (IC) measurement, degradation rate and the defluorinate of PFOA are calculated with this
Rate, specific degradation and defluorinate curve are as shown in figures 5 c and 5d.
From this it can be concluded that the degradation and defluorinate of PFOA are hardly influenced by pH value of solution in reaction.
Embodiment 5
The basic content of the present embodiment is with embodiment 3, the difference is that the efficient degradation perfluorochemical of the present embodiment
Step (5) in method specifically:
Before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution are uniformly mixed first, then by 0.6MOM-MMT points
It is scattered in the mixed solution of IAA and PFOA, the content for obtaining IAA, PFOA and montmorillonite is respectively 2mM, 10mg/L and 2.2g/L
Reaction solution.Then the pH to 7.0 that reaction solution is adjusted using the NaOH and HCl of 0.1mM, it is molten to reaction using magnetic agitation
Liquid stirs 30 minutes, and reaction solution is transferred in crystal reaction tube after stirring, and overall reaction liquid product is 300ml, by one
Small cup 36W mercury lamp is immersed into reaction solution, is turned on light and is carried out degradation reaction.Reaction temperature control is at 25 ± 2 DEG C, the reaction time 14
Hour.Sample time is respectively set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h, 14h.Sample passes through SPE
In-between product is detected and quantifies using LC/MS/MS after column processing, it is as shown in Figure 6 that intermediate product changes over time curve.
From this it can be concluded that the intermediates of PFOA mainly include the perfluorocarboxylic acid of different chain length in the system
And acetic acid methane.
Embodiment 6
The basic content of the present embodiment is with embodiment 3, the difference is that the efficient degradation perfluorochemical of the present embodiment
Step (5) in method is the case where aqueous electron degrades to PFOA in the presence of investigating different anions, concrete operation step are as follows:
Before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution are uniformly mixed first, then by 0.6MOM-MMT points
It is scattered in the mixed solution of IAA and PFOA, the content for obtaining IAA, PFOA and montmorillonite is respectively 2mM, 10mg/L and 2.2g/L
Reaction solution.Then the pH to 7.0 that reaction solution is adjusted using the NaOH and HCl of 0.1mM, is added in two groups of experiments respectively
1mM NO3 -And SO4 2-.Reaction solution is stirred 30 minutes using magnetic agitation, reaction solution is transferred to quartz after stirring
In reaction tube, overall reaction liquid product is 300ml, and a 36W mercury lamp is immersed into reaction solution, turns on light and carries out degradation reaction.
At 25 ± 2 DEG C, the reaction time is 14 hours for reaction temperature control.Sample time be respectively set to 0h, 0.5h, 1.5h, 2.5h,
3.5h,4.5h,6h,8h,11h,14h.Sample is divided into two parts, with high performance liquid chromatography after the acetonitrile extraction of a 2 times of volumes
(HPLC) residue PFOA content is measured, the F ion content generated after another filtering with ion chromatography (IC) measurement is calculated with this
The degradation rate and defluorinate rate of PFOA, specific degradation and defluorinate curve are as shown in Figure 7.
From this it can be concluded that the presence of water body nitrate anion and sulfate radical does not almost have an impact the reaction.
Embodiment 7
A kind of method of efficient degradation perfluorochemical, the steps include:
(1) 200g montmorillonite (being purchased from Zhejiang Feng Hong montmorillonite Chemical Co., Ltd.) is dispersed in 4L water, is added
0.4mol solid NaCl is saturated 8h, and centrifugation discards supernatant liquid, obtains sediment；Sediment is redispersed in 4L water, so weight
It operates 6 times again.Sediment is cleaned with deionized water, is washed till with AgNO3Solution detection is generated without precipitating.Freeze-drying is satisfied
The Na of sum+Montmorillonite；
(2) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
Total amount of electric charge is added in de- soil solution and exchanges the consistent poly- 4-vinylpridine benzene second of total amount with the cation of montmorillonite in solution
Alkene (is dissolved in 5mol/L H2SO4) aqueous solution 50mL, it stirs 24 hours, centrifugation obtains sediment, washes with water sediment, obtains
Poly- 4-vinylpridine styrene montmorillonite (PVPcoS-MMT)；
(3) the phenylethene modified montmorillonite of poly- 4-vinylpridine is dispersed in water, is stirred 1 hour.It stirs evenly
Afterwards, 0.2CEC, 0.4CEC, 0.6CEC, 0.8CEC are separately added into scattered poly- 4-vinylpridine styrene montmorillonite
The cetyl trimethyl bromination ammonia solution of amount stirs 24 hours, and centrifugation obtains sediment, washes with water sediment, is mixed
It closes modified organo montmorillonite (0.2MOM-MMT, 0.4MOM-MMT, 0.6MOM-MMT, 0.8MOM-MMT)；
(4) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
The cetyl trimethyl bromination ammonia spirit of 1CEC is added in de- soil solution, stirs 24 hours, centrifugation obtains sediment, spends
Ionized water water cleans sediment, obtains cetyl trimethyl ammonia bromide modified montmorillonoid (HDTMA-MMT)；
(5) it is transferred in 20ml glass tube, uses after first mixing prepared heteroauxin solution and montmorillonite
The NaOH and HCl of 0.1mM adjusts the pH to 7.0 of solution, is added aqueous electron capturing agent dimethyl pyridine N-oxide (DMPO).
Reaction total volume is 10mL, and wherein the concentration of heteroauxin and DMPO are respectively 2mM and 20mM, and montmorillonite concentration is 2.2g/L.
After 180W Hg lamp irradiation 3.5min, 20 μ L of sampling, which are put into electron paramagnetic resonance (EPR), detects Free Radical Signal, specific as schemed
Shown in 8.
From this it can be concluded that the active specy in solution is mainly hydroxyl in the presence of without montmorillonite, na montmorillonite
Free radical, therefore can't detect the signal of aqueous electron in sample, after being added to organo montmorillonite, is removed in sample and detect hydroxyl
Outside base free radical, while also detecting that the signal of aqueous electron, it is mixed and modified in HDTMA modified montmorillonite and 0.6MOM
Stronger water and electronic signal are all detected in montmorillonite.In the modified montmorillonite of PVPcoS, hydroxyl free is detected
Base signal and weaker aqueous electron signal.This illustrates that the presence of HDTMA protects aqueous electron not quenched by oxygen, therefore
Promote degradation and defluorinate of the aqueous electron to perfluorochemical.
Claims (10)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910197900.2A CN109745962A (en) | 2019-03-15 | 2019-03-15 | A kind of mixed modified organic montmorillonite and its synthesis method and application |
| PCT/CN2019/118710 WO2020186795A1 (en) | 2019-03-15 | 2019-11-15 | Mixed modified organic montmorillonite, synthesis method thereof, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910197900.2A CN109745962A (en) | 2019-03-15 | 2019-03-15 | A kind of mixed modified organic montmorillonite and its synthesis method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109745962A true CN109745962A (en) | 2019-05-14 |
Family
ID=66408702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910197900.2A Pending CN109745962A (en) | 2019-03-15 | 2019-03-15 | A kind of mixed modified organic montmorillonite and its synthesis method and application |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109745962A (en) |
| WO (1) | WO2020186795A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153462A (en) * | 2020-01-14 | 2020-05-15 | 南京大学 | A method of degrading perfluorinated compounds |
| CN111468073A (en) * | 2020-04-03 | 2020-07-31 | 江南大学 | Dephosphorization reagent for air floatation and preparation method thereof |
| CN111518011A (en) * | 2020-04-29 | 2020-08-11 | 南京大学 | A kind of synthetic method and application of indole derivatives capable of efficiently degrading perfluorinated compounds |
| WO2020186795A1 (en) * | 2019-03-15 | 2020-09-24 | 南京大学 | Mixed modified organic montmorillonite, synthesis method thereof, and application thereof |
| CN114832777A (en) * | 2022-05-11 | 2022-08-02 | 浙江大学 | Modification method for removing perfluorocarboxylic acid in water by using enhanced activated carbon and prepared modified activated carbon |
| CN116573711A (en) * | 2023-05-15 | 2023-08-11 | 苏州科技大学 | A kind of polybenzazole-montmorillonite complex and its preparation method and application |
| EP4061869A4 (en) * | 2019-11-08 | 2023-11-01 | Board Of Trustees Of Michigan State University | NANOREACTOR SYSTEM FOR THE DECOMPOSITION OF PER- AND POLYFLUORALKYL SUBSTANCES |
| US12275661B2 (en) | 2023-07-14 | 2025-04-15 | Claros Technologies Inc. | Methods and systems of iodine capture from aqueous solutions |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116178789A (en) * | 2023-03-01 | 2023-05-30 | 宁波瑞成包装材料有限公司 | Modified montmorillonite and polypropylene film |
| CN118142498B (en) * | 2024-05-09 | 2024-07-30 | 中国科学院合肥物质科学研究院 | A composite material with interlayer confined structure and its preparation method and application |
| CN119430342B (en) * | 2024-10-12 | 2025-04-01 | 中安智创环保科技有限公司 | Recyclable defluorinating agent and preparation method thereof |
| CN119101018B (en) * | 2024-11-08 | 2025-01-21 | 山东东悦新材料科技股份有限公司 | Continuous production method of glycidyl methacrylate |
| CN119746805A (en) * | 2024-12-20 | 2025-04-04 | 华东理工大学 | A multi-layer modified vermiculite material for adsorbing PFOA and a preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438255A (en) * | 2003-03-13 | 2003-08-27 | 上海交通大学 | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer |
| CN1224718C (en) * | 2004-01-12 | 2005-10-26 | 陕西科技大学 | Preparation technology of ving/polymer/modified montmorillonoid nano composite tanoing agent |
| CN101027347A (en) * | 2004-09-27 | 2007-08-29 | 3M创新有限公司 | Method of making a composition and nanocomposites therefrom |
| CN103764572A (en) * | 2011-06-23 | 2014-04-30 | 加维什-加利利生物应用有限公司 | Method for pretreatment of wastewater and recreational water with nanocomposites |
| CN105536198A (en) * | 2015-12-23 | 2016-05-04 | 南京大学 | Method for efficiently degrading perfluorinated compounds (PFCs) |
| CN106495175A (en) * | 2016-12-23 | 2017-03-15 | 仲恺农业工程学院 | Preparation method of organic modified montmorillonite |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9936692B2 (en) * | 2012-02-14 | 2018-04-10 | University Of Florida Research Foundation, Inc. | Engineered particulate systems for controlled release of pesticides and repellants |
| CN104987727B (en) * | 2015-07-20 | 2017-09-26 | 上海工程技术大学 | A kind of preparation method of the silicon rubber containing organic modification montmonrillonite |
| CN109745962A (en) * | 2019-03-15 | 2019-05-14 | 南京大学 | A kind of mixed modified organic montmorillonite and its synthesis method and application |
-
2019
- 2019-03-15 CN CN201910197900.2A patent/CN109745962A/en active Pending
- 2019-11-15 WO PCT/CN2019/118710 patent/WO2020186795A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438255A (en) * | 2003-03-13 | 2003-08-27 | 上海交通大学 | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer |
| CN1216085C (en) * | 2003-03-13 | 2005-08-24 | 上海交通大学 | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer |
| CN1224718C (en) * | 2004-01-12 | 2005-10-26 | 陕西科技大学 | Preparation technology of ving/polymer/modified montmorillonoid nano composite tanoing agent |
| CN101027347A (en) * | 2004-09-27 | 2007-08-29 | 3M创新有限公司 | Method of making a composition and nanocomposites therefrom |
| CN103764572A (en) * | 2011-06-23 | 2014-04-30 | 加维什-加利利生物应用有限公司 | Method for pretreatment of wastewater and recreational water with nanocomposites |
| CN105536198A (en) * | 2015-12-23 | 2016-05-04 | 南京大学 | Method for efficiently degrading perfluorinated compounds (PFCs) |
| CN106495175A (en) * | 2016-12-23 | 2017-03-15 | 仲恺农业工程学院 | Preparation method of organic modified montmorillonite |
Non-Patent Citations (1)
| Title |
|---|
| 陈张浩等: ""有机粘土促进下全氟辛酸降解研究"", 《持久性有机污染物论坛 2017 暨第十二届持久性有机污染物学术研讨会论文集》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020186795A1 (en) * | 2019-03-15 | 2020-09-24 | 南京大学 | Mixed modified organic montmorillonite, synthesis method thereof, and application thereof |
| EP4061869A4 (en) * | 2019-11-08 | 2023-11-01 | Board Of Trustees Of Michigan State University | NANOREACTOR SYSTEM FOR THE DECOMPOSITION OF PER- AND POLYFLUORALKYL SUBSTANCES |
| AU2020378491B2 (en) * | 2019-11-08 | 2024-05-23 | Board Of Trustees Of Michigan State University | Nano-reactor system for decomposition of per- and polyfluoroalkyl substances |
| CN111153462A (en) * | 2020-01-14 | 2020-05-15 | 南京大学 | A method of degrading perfluorinated compounds |
| WO2021143454A1 (en) * | 2020-01-14 | 2021-07-22 | 南京大学 | Method for degrading perfluorinated compound |
| CN111468073A (en) * | 2020-04-03 | 2020-07-31 | 江南大学 | Dephosphorization reagent for air floatation and preparation method thereof |
| CN111468073B (en) * | 2020-04-03 | 2021-06-25 | 江南大学 | A kind of phosphorus removal agent for air flotation and preparation method thereof |
| CN111518011B (en) * | 2020-04-29 | 2021-02-12 | 南京大学 | A kind of synthetic method and application of indole derivatives capable of efficiently degrading perfluorinated compounds |
| US11795076B2 (en) | 2020-04-29 | 2023-10-24 | Nanjing University | Synthesis method of indole derivative capable of efficiently degrading perfluorinated compound (PFC) |
| WO2021218570A1 (en) * | 2020-04-29 | 2021-11-04 | 南京大学 | Method for synthesizing indole derivative capable of efficiently degrading perfluorinated compound and application thereof |
| CN111518011A (en) * | 2020-04-29 | 2020-08-11 | 南京大学 | A kind of synthetic method and application of indole derivatives capable of efficiently degrading perfluorinated compounds |
| CN114832777A (en) * | 2022-05-11 | 2022-08-02 | 浙江大学 | Modification method for removing perfluorocarboxylic acid in water by using enhanced activated carbon and prepared modified activated carbon |
| CN116573711A (en) * | 2023-05-15 | 2023-08-11 | 苏州科技大学 | A kind of polybenzazole-montmorillonite complex and its preparation method and application |
| CN116573711B (en) * | 2023-05-15 | 2023-10-10 | 苏州科技大学 | A polyindole-montmorillonite composite and its preparation method and application |
| US12275661B2 (en) | 2023-07-14 | 2025-04-15 | Claros Technologies Inc. | Methods and systems of iodine capture from aqueous solutions |
| US12351498B2 (en) | 2023-07-14 | 2025-07-08 | Claros Technologies Inc. | Methods and systems of PFAS destruction using UV irradiation at 222 nanometers |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020186795A1 (en) | 2020-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109745962A (en) | A kind of mixed modified organic montmorillonite and its synthesis method and application | |
| CN105536198B (en) | A kind of method of efficient degradation perfluorochemical | |
| Du et al. | Selective and high sorption of perfluorooctanesulfonate and perfluorooctanoate by fluorinated alkyl chain modified montmorillonite | |
| Yan et al. | Degradation of trichloroethylene by activated persulfate using a reduced graphene oxide supported magnetite nanoparticle | |
| Wang et al. | A magnetic γ-Fe 2 O 3@ PANI@ TiO 2 core–shell nanocomposite for arsenic removal via a coupled visible-light-induced photocatalytic oxidation–adsorption process | |
| Yang et al. | Flocculation performance and mechanism of graphene oxide for removal of various contaminants from water | |
| Wang et al. | Biosorption of multifold toxic heavy metal ions from aqueous water onto food residue eggshell membrane functionalized with ammonium thioglycolate | |
| Hao et al. | Magnetic field assisted adsorption of methyl blue onto organo-bentonite | |
| Chen et al. | Application of surfactant modified montmorillonite with different conformation for photo-treatment of perfluorooctanoic acid by hydrated electrons | |
| Al-Kahtani et al. | Photocatalytic degradation of Maxilon CI basic dye using CS/CoFe2O4/GONCs as a heterogeneous photo-Fenton catalyst prepared by gamma irradiation | |
| Jing et al. | Adsorption of 2-mercaptobenzothiazole from aqueous solution by organo-bentonite | |
| CN101780985A (en) | Hydrotalcite-like compound used for raw water treatment | |
| Gharaghani et al. | Photocatalytic degradation of the antibiotic ciprofloxacin by ZnO nanoparticles immobilized on a glass plate | |
| CN106732435A (en) | A kind of Fe3O4The method that the co-precipitation of/shitosan prepares chitosan magnetic adsorbent | |
| Liu et al. | Heterogeneous degradation of tetracycline by magnetic Ag/AgCl/modified zeolite X–persulfate system under visible light | |
| Samuel et al. | Photocatalytic degradation of perfluoroalkyl substances in water by using a duo-functional tri-metallic-oxide hybrid catalyst | |
| Danesh et al. | Sulfonic acid functionalized magnetite nanoporous-KIT-6 for removal of methyl green from aqueous solutions | |
| Wan et al. | Effective adsorption of bisphenol A from aqueous solution over a novel mesoporous carbonized material based on spent bleaching earth | |
| Tran et al. | Boosting tetracycline degradation by integrating MIL-88A (Fe) with CoFe2O4 persulfate activators | |
| Xu et al. | Degradation of methyl orange in aqueous solution by microwave irradiation in the presence of granular-activated carbon | |
| Wei et al. | Effect of environmental factors on enhanced adsorption and photocatalytic regeneration of molecular imprinted TiO2 polymers for fluoroquinolones | |
| Nie et al. | Natural alumina/silica suspended particles in water to enhance ofloxacin degradation with UVA-H2O2 driven by surface chemistry | |
| Wang et al. | Fabrication of resin supported Au–Pd bimetallic nanoparticle composite to efficiently remove chloramphenicol from water | |
| Mahmoud et al. | Efficient and fast microwave sorption of heavy metals on nanosilica sorbents-microwave immobilized-vitamin C and vitamin L1 | |
| Zhang et al. | Kinetics and mechanisms of flumequine degradation by sulfate radical based AOP in different water samples containing inorganic anions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190514 |
|
| WD01 | Invention patent application deemed withdrawn after publication |