CN116272919B - Method for detecting by-products of water disinfection - Google Patents
Method for detecting by-products of water disinfection Download PDFInfo
- Publication number
- CN116272919B CN116272919B CN202310566378.7A CN202310566378A CN116272919B CN 116272919 B CN116272919 B CN 116272919B CN 202310566378 A CN202310566378 A CN 202310566378A CN 116272919 B CN116272919 B CN 116272919B
- Authority
- CN
- China
- Prior art keywords
- acid
- vinyl
- monomer
- magnetic
- quaternary ammonium
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000006227 byproduct Substances 0.000 title claims abstract description 17
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 58
- 238000000605 extraction Methods 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 12
- 239000003480 eluent Substances 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 84
- 238000002360 preparation method Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 150000003138 primary alcohols Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 10
- 239000002841 Lewis acid Substances 0.000 claims description 9
- -1 carboxyl anions Chemical class 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 150000007517 lewis acids Chemical class 0.000 claims description 9
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 9
- 150000003333 secondary alcohols Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000007142 ring opening reaction Methods 0.000 claims description 8
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 3
- JHYKJJIJPWNOME-UHFFFAOYSA-N 1,4a,8-triazido-2,3,4,5,6,7-hexahydro-1H-naphthalene Chemical compound N(=[N+]=[N-])C12CCCC(=C2C(CCC1)N=[N+]=[N-])N=[N+]=[N-] JHYKJJIJPWNOME-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007171 acid catalysis Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000005815 base catalysis Methods 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 3
- 238000007265 chloromethylation reaction Methods 0.000 claims description 3
- UNXNGGMLCSMSLH-UHFFFAOYSA-N dihydrogen phosphate;triethylazanium Chemical compound OP(O)(O)=O.CCN(CC)CC UNXNGGMLCSMSLH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000000269 nucleophilic effect Effects 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- GJFNRSDCSTVPCJ-UHFFFAOYSA-N 1,8-bis(dimethylamino)naphthalene Chemical compound C1=CC(N(C)C)=C2C(N(C)C)=CC=CC2=C1 GJFNRSDCSTVPCJ-UHFFFAOYSA-N 0.000 claims 1
- 238000010828 elution Methods 0.000 claims 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 abstract description 7
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 description 18
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- SIEILFNCEFEENQ-UHFFFAOYSA-N dibromoacetic acid Chemical compound OC(=O)C(Br)Br SIEILFNCEFEENQ-UHFFFAOYSA-N 0.000 description 6
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical compound OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229960005215 dichloroacetic acid Drugs 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- XVOAHPOEMCETJM-UHFFFAOYSA-N 1-n,8-n-dimethylnaphthalene-1,8-diamine Chemical compound C1=CC(NC)=C2C(NC)=CC=CC2=C1 XVOAHPOEMCETJM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
-
- 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
- B01J20/22—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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of haloacetic acid solid-phase extraction, and discloses a detection method for water disinfection byproducts, wherein the method adopts a liquid chromatography-mass spectrometry online method to detect the haloacetic acid which is a water disinfection byproduct, the haloacetic acid is extracted by using a magnetic extractant ME, and the specific extraction steps are as follows: adding a magnetic extractant ME and a Lewis acid catalyst into a water quality sample to be measured, stirring and extracting, enriching the magnetic extractant ME by using an external magnetic field, taking out the magnetic extractant ME, eluting haloacetic acid by using an eluent, drying by nitrogen, and re-dissolving by using a mobile phase to be used as a sample sampled by a liquid phase mass spectrometer. The invention provides a magnetic extractant ME for extracting haloacetic acid, which can be used for extracting the haloacetic acid, and the extraction capacity of the magnetic extractant ME can be remarkably improved by adding a Lewis acid catalyst when the haloacetic acid is extracted under the stirring action. The invention also provides a haloacetic acid solid-phase extraction method based on the magnetic extractant ME.
Description
Technical Field
The invention relates to the technical field of haloacetic acid solid phase extraction, in particular to a detection method for a water disinfection by-product.
Background
Haloacetic acid is a major class of disinfection by-products in chlorinated disinfected drinking water, which is listed as a routine monitoring project for drinking water due to the broad and potential health hazards that exist. Currently, research on determination of haloacetic acid compounds in water is mainly focused on gas chromatography-mass spectrometry (GC/MS), ion chromatography and liquid chromatography-mass spectrometry. The liquid chromatography-mass spectrometry online pretreatment process is simple, the sample does not need to be derived, the method has high sensitivity, and the method is a detection method with prospect, but the concentration of haloacetic acid in drinking water is generally [ mu ] g/L or even lower, so that the sample needs to be subjected to enrichment pretreatment before analysis and detection by adopting the liquid chromatography-mass spectrometry online method.
Disclosure of Invention
The invention provides a method for solid phase extraction of haloacetic acid, which takes the haloacetic acid obtained by solid phase extraction pre-enrichment as a sample injected by a liquid chromatography-mass spectrometry online method.
The method for detecting the water disinfection byproducts comprises the steps of detecting the water disinfection byproducts haloacetic acid by adopting a liquid chromatography-mass spectrometry online method, extracting the haloacetic acid by utilizing a magnetic extractant ME, wherein the specific extraction steps are as follows: adding a magnetic extractant ME and a Lewis acid catalyst into a water quality sample to be measured, stirring and extracting, enriching the magnetic extractant ME by using an external magnetic field, taking out the magnetic extractant ME, eluting haloacetic acid by using an eluent, drying by nitrogen, and re-dissolving by using a mobile phase to be used as a sample sampled by a liquid phase mass spectrometer;
the preparation method of the magnetic extractant ME comprises the following steps:
step S1, preparing a hydroxyl@quaternary ammonium salt functional monomer, wherein the preparation steps are as follows:
s1-1, preparation of trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 ；
S1-2 Sulfur functionality Using a thiolating reagent with a trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 Nucleophilic substitution reaction of chloromethyl functional group, hydrolysis reaction in alkaline solution, and preparation of trimercapto monomer M-Vinyl- (SH) 3 ；
S1-3 by means of a trimercapto monomer M-Vinyl- (SH) 3 The sulfhydryl functional group of (2) and the epoxy functional group of 2, 3-epoxypropyl trimethyl ammonium chloride undergo a ring-opening reaction to generate a hydroxyl@quaternary ammonium salt functional monomer;
step S2, self-assembling quaternary ammonium positive ions of hydroxyl@quaternary ammonium salt functional monomers and carboxyl anions of haloacetic acid through electrostatic acting force;
step S3, carrying out esterification reaction on hydroxyl functional groups of the hydroxyl@quaternary ammonium salt functional monomer and carboxyl functional groups of the haloacetic acid under the catalysis of Lewis acid to obtain a haloacetic acid template functional monomer M-Vinyl;
step S4, grafting and polymerizing the haloacetic acid template functionalized monomer M-Vinyl to Fe modified by methacryloxy functional groups under the action of an initiator and a crosslinking agent 3 O 4 And eluting the haloacetic acid template from the surface of the magnetic nano particles to prepare the magnetic extractant ME.
Preferably, the eluent of the haloacetic acid consists of 5-15 wt% of NaCl and 1-5 wt% of NaOH.
Preferably, the mobile phase used for the haloacetic acid reconstitution is phosphoric acid-triethylamine buffer with ph=3.2 and methanol.
Preferably, the trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 The preparation method of (2) is as follows: using styrene as raw material, using paraformaldehyde and hydrochloric acid as chloromethylation reagent, under the synergistic catalysis of protonic acid and Lewis acid, making polychloromethylation reaction on aromatic ring of styrene to obtain trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 。
Preferably, the Lewis acid may be selected from ZnCl 2 、SnCl 4 、FeCl 3 、AlCl 3 One or a combination of more than one of them.
Preferably, the hydroxyl group@quaternary ammonium salt functionalized monomer comprises: primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + And/or secondary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + )。
Preferably, the primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + The preparation method of (2) is as follows: by utilizing the acid catalysis mechanism of mercapto-epoxy reaction, under the action of Lewis acid catalyst, through trimercapto monomer M-Vinyl- (SH) 3 The sulfhydryl functional group of (2) and the epoxy functional group of 2, 3-epoxypropyl trimethyl ammonium chloride undergo ring opening reactionThe primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) is generated 2 OH)-N + 。
Preferably, the lewis acid catalyst is selected from one or more of boric acid, phenylboric acid and pentafluorophenylboric acid.
Preferably, the secondary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + The preparation method of (2) is as follows: by utilizing the base catalysis mechanism of mercapto-epoxy reaction, under the action of organic base catalyst, through trimercapto monomer M-Vinyl- (SH) 3 The sulfhydryl function of (2) and the epoxy function of 2, 3-epoxypropyl trimethyl ammonium chloride occur in accordance with SN 2 Click chemistry reaction of nucleophilic ring opening mechanism to produce secondary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + 。
Preferably, the organic base catalyst is selected from one or more of tetrabutylammonium fluoride, 1,5, 7-triazido bicyclo (4.4.0) dec-5-ene and 1, 8-dimethylamino naphthalene.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention synthesizes a hydroxyl@quaternary ammonium salt functional monomer (primary alcohol@quaternary ammonium salt functional monomer M-Vinyl- (CH) 2 OH)-N + And a secondary alcohol @ quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + ) On one hand, the quaternary ammonium positive ion of the hydroxyl group@quaternary ammonium salt functional monomer and the carboxyl negative ion of the haloacetic acid are self-assembled through electrostatic acting force, and on the other hand, the hydroxyl functional group of the hydroxyl group@quaternary ammonium salt functional monomer and the carboxyl functional group of the haloacetic acid are subjected to esterification reaction under the catalysis of Lewis acid to prepare the haloacetic acid template functional monomer M-Vinyl;
the haloacetic acid template functionalized monomer M-Vinyl is graft polymerized to Fe modified by methacryloxy functional group under the action of an initiator and a crosslinking agent 3 O 4 Eluting the haloacetic acid template from the surface of the magnetic nano particles to prepare a magnetic extractant ME;
the extraction experiment of the magnetic extractant ME on haloacetic acid is known: magnetic extractants can be used to extract haloacetic acids; and the Lewis acid catalyst is added when the haloacetic acid is extracted under the stirring action, so that the extraction capacity of the magnetic extractant can be obviously improved.
The invention provides a magnetic extractant for extracting haloacetic acid and provides a haloacetic acid solid-phase extraction method based on the magnetic extractant.
Drawings
FIG. 1 is a schematic illustration of the trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 A chemical structural formula of (a);
FIG. 2 is a diagram of a trimercapto monomer M-Vinyl- (SH) 3 A chemical structural formula of (a);
FIG. 3 is a primary alcohol @ quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + A chemical structural formula of (a);
FIG. 4 is a secondary alcohol @ quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + A chemical structural formula of (a);
fig. 5 is a bar graph of the results of the extraction experiment of magnetic extractant ME with respect to trichloroacetic acid.
Detailed Description
Example 1
Preparation of trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 The synthesis mechanism is as follows: using styrene as raw material, using paraformaldehyde and hydrochloric acid as chloromethylation reagent, under the synergistic catalysis of protonic acid and Lewis acid, making polychloromethylation reaction on aromatic ring of styrene to obtain trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 ；
Wherein the Lewis acid is ZnCl 2 、SnCl 4 、FeCl 3 、AlCl 3 One or a combination of more than one of them; concentrated sulfuric acid is preferably used as the protonic acid;
trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 The specific synthesis steps of (a) are as follows: into a 250mL four-necked flask equipped with a mechanical stirrer, a reflux condenser, a thermometer and a tail gas treatment device, 1g of styrene, 7.28g of paraformaldehyde, 10mL of concentrated hydrochloric acid, 30mL of concentrated sulfuric acid, 6.5g of FeCl were charged 3 Stirring, placing in water bath, mechanically stirring at 75deg.C for reaction for 20 hr, cooling to room temperature after reaction, filtering to collect solid product, and deionizedWashing with water, and vacuum drying at 40deg.C to constant weight to obtain trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 The chemical structural formula of the catalyst is shown in figure 1;
trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 The nuclear magnetic resonance spectrum of (2) shows that:
1 H NMR(400MHz，CDCl 3 )，δ：4.46(s，2H，-CH 2 -)，4.49(s，2H，-CH 2 -)，4.53(s，2H，-CH 2 -)，5.51(dd，1H，=CH 2 )，5.74(dd，1H，=CH 2 )，6.98(s，2H，Ar-H)，7.12(dd，1H，-CH=)；
13 C NMR(101MHz，CDCl 3 )，δ：44.7(2C，-CH 2 -)，46.8(1C，-CH 2 -)，118.2(1C，=CH 2 ) 134.5 (1C, -ch=), 130.0 (2C, benzene ring carbon), 135.9 (2C, benzene ring carbon), 136.8 (1C, benzene ring carbon), 137.4 (1C, benzene ring carbon).
Example 2
Trimercapto monomer M-Vinyl- (SH) 3 The synthesis mechanism is as follows: a thiolating agent is used and the sulfur function through the thiolating agent is first directly reacted with the trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 Nucleophilic substitution reaction of chloromethyl functional group, and then hydrolysis reaction in alkaline solution, to obtain trimercapto monomer M-Vinyl- (SH) 3 ；
Wherein, thiothiourea, thioacetic acid and sodium thiosulfate can be selected and used as the sulfhydrylation reagent;
trimercapto monomer M-Vinyl- (SH) 3 The specific synthesis steps of (a) are as follows: into a 250mL four-necked flask equipped with a mechanical stirrer, reflux condenser, thermometer and nitrogen protection device, 1.2g of trimercapto monomer M-Vinyl- (SH) was first added 3 2.21g of thiourea and 50mL of absolute ethyl alcohol, reflux-stirring and reacting for 4 hours at 50 ℃, adding 25g of sodium hydroxide, continuing reflux-stirring and reacting for 12 hours at 50 ℃ under the protection of nitrogen, cooling to room temperature after the reaction is finished, washing a product by using deionized water until the washing liquid is neutral, and vacuum-drying at 40 ℃ until the weight is constant to obtain a trimercapto monomer M-Vinyl- (SH) 3 The chemical structural formula is shown in figure 2;
trimercapto monomer M-Vinyl- (SH) 3 The nuclear magnetic resonance spectrum of (2) shows that:
1 H NMR(400MHz，CDCl 3 )，δ：1.74-1.85(m，3H，-SH)，3.78-3.99(m，6H，-CH 2 -)，5.49(dd，1H，=CH 2 )，5.71(dd，1H，=CH 2 )，6.67(s，2H，Ar-H)，7.13(dd，1H，-CH=)；
13 C NMR(101MHz，CDCl 3 )，δ：26.5(2C，-CH 2 -)，28.6(1C，-CH 2 -)，118.2(1C，=CH 2 ) 126.6 (2C, carbon benzoring), 133.4 (1C, carbon benzoring), 134.5 (1C, -ch=), 138.8 (1C, carbon benzoring), 142.1 (2C, carbon benzoring).
Example 3
Preparation of primary alcohol @ quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + The synthesis mechanism is as follows: by utilizing the acid catalysis mechanism of mercapto-epoxy reaction, under the action of Lewis acid catalyst, through trimercapto monomer M-Vinyl- (SH) 3 The sulfhydryl functional group of (2) and the epoxy functional group of 2, 3-epoxypropyl trimethyl ammonium chloride undergo a regional ring-opening reaction to generate a primary alcohol@quaternary ammonium salt functional monomer M-Vinyl- (CH) 2 OH)-N + ；
Wherein, the Lewis acid catalyst is selected from one or more of boric acid, phenylboric acid and pentafluorophenylboric acid;
primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + The specific synthesis steps of (a) are as follows: into a 250mL four-necked flask equipped with a mechanical stirrer, reflux condenser, thermometer and nitrogen protection device, 1g of trimercapto monomer M-Vinyl- (SH) was charged 3 3.8g of 2, 3-epoxypropyl trimethyl ammonium chloride, 0.5g of phenylboric acid and 30mL of toluene solvent are continuously stirred and introduced with nitrogen for reflux stirring reaction for 24 hours at 60 ℃, after the reaction is finished, the mixture is cooled to room temperature, acetone is added for precipitation separation, the precipitation product is dissolved by ethanol and is separated by acetone precipitation again, and the mixture is dried in vacuum at 40 ℃ to constant weight to obtain the primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + The chemical structural formula is shown in figure 3;
primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + The nuclear magnetic resonance hydrogen spectrum of (2) shows that: 1 H NMR(400MHz，CDCl 3 )，δ：1.83(s，3H，-OH)，2.31(s，27H，-CH 3 )，2.60-2.79(m，6H，-CH 2 -)，3.70(s，6H，-CH 2 -)，3.71-3.96(m，6H，-CH 2 -)，2.41-2.54(m，3H，-CH-)，5.51(dd，1H，=CH 2 )，5.73(dd，1H，=CH 2 )，6.67(s，2H，Ar-H)，7.12(dd，1H，-CH=)。
example 4
Preparation of Secondary alcohol @ Quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + The synthesis mechanism is as follows: by utilizing the base catalysis mechanism of mercapto-epoxy reaction, under the action of organic base catalyst, through trimercapto monomer M-Vinyl- (SH) 3 The sulfhydryl function of (2) and the epoxy function of 2, 3-epoxypropyl trimethyl ammonium chloride occur in accordance with SN 2 Click chemistry reaction of nucleophilic ring opening mechanism to produce secondary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + ；
Wherein, the organic base catalyst is selected from one or more than one of tetrabutylammonium fluoride, 1,5, 7-triazido bicyclo (4.4.0) dec-5-ene and 1, 8-dimethylamino naphthalene;
secondary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + The specific synthesis steps of (a) are as follows: into a 250mL four-necked flask equipped with a mechanical stirrer, reflux condenser, thermometer and nitrogen protection device, 1g of trimercapto monomer M-Vinyl- (SH) was charged 3 3.8g of 2, 3-epoxypropyl trimethyl ammonium chloride, 1.1g of tetrabutylammonium fluoride, 20mL of absolute ethyl alcohol and 10mL of deionized water are continuously stirred and introduced with nitrogen protection, reflux stirring is carried out at 60 ℃ for 12h, after the reaction is finished, cooling is carried out to room temperature, acetone is added for precipitation separation, the precipitation product is dissolved by ethanol and is separated by acetone precipitation again, vacuum drying is carried out at 40 ℃ until the weight is constant, and the secondary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N is obtained + The chemical structural formula is shown in figure 4;
secondary alcohol @ quaternary ammonium salt functionalized monomerM-Vinyl-(CHOH)-N + The nuclear magnetic resonance hydrogen spectrum of (2) shows that: 1 H NMR(400MHz，CDCl 3 )，δ：2.15(s，3H，-OH)，2.27(s，27H，-CH 3 )，2.37-2.69(m，12H，-CH 2 -)，3.74(s，6H，-CH 2 -)，3.82(m，3H，-CH-)，5.50(dd，1H，=CH 2 )，5.74(dd，1H，=CH 2 )，6.65(s，2H，Ar-H)，7.12(dd，1H，-CH=)。
example 5
Preparation of methacryloxy functional group modified Fe 3 O 4 The preparation method of the magnetic nanoparticle comprises the following specific steps:
in a 250mL three-necked flask equipped with a mechanical stirrer, thermometer and nitrogen blanket, 100mL of deionized water was first added followed by 12g of FeCl 3 ·6H 2 O、6gFeCl 2 ·4H 2 O, stirring for 1h, adding 20mL of ammonia water, mechanically stirring at 65deg.C under nitrogen protection for reacting for 1h, cooling to room temperature, centrifuging to remove large particles, dialyzing with dialysis bag (MWCO: 14000) for 24h, removing unreacted substances, and vacuum drying at 50deg.C to obtain Fe 3 O 4 Magnetic nanoparticles;
3g of Fe 3 O 4 The magnetic nano particles are dispersed in 30mL of 3- (methacryloyloxy) propyl trimethoxy silane in 100mL of anhydrous toluene under the protection of nitrogen, reacted for 24 hours at 70 ℃, the product is collected by a magnet, washed by ethanol and deionized water and dried to constant weight, and Fe modified by methacryloyloxy functional groups is obtained 3 O 4 Magnetic nanoparticles.
Example 6
The preparation mechanism of the magnetic extractant ME-I is as follows:
in one aspect, the primary alcohol @ quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + Self-assembling the quaternary ammonium positive ions of the (E) and the carboxyl negative ions of the haloacetic acid through electrostatic acting force;
on the other hand, the primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + The primary alcohol functional group of (2) and the carboxyl functional group of haloacetic acid are subjected to esterification reaction under the catalysis of Lewis acidPreparing a haloacetic acid template functionalized monomer M-Vinyl-I;
under the action of initiator and cross-linking agent, haloacetic acid template functional monomer M-Vinyl-I is grafted and polymerized to Fe modified by methacryloxy functional group 3 O 4 The surface of the magnetic nano particle is eluted to remove the haloacetic acid template, and the magnetic extractant ME-I is prepared;
the preparation method of the magnetic extractant ME-I comprises the following steps:
in a three-necked flask equipped with a water separator, thermometer and reflux condenser, 3g of trichloroacetic acid, 2g of primary alcohol @ quaternary ammonium salt functionalized monomer M-Vinyl- (CH) were first added 2 OH)-N + 100mL deionized water, stirring and mixing for 1h, performing electrostatic self-assembly, and then adding 0.2g FeCl 3 Reflux-reacting catalyst and 8mL cyclohexane water-carrying agent at 60 ℃ for 3h, separating water until no water is separated out, and adding 3g of Fe modified by methacryloxy functional group 3 O 4 The magnetic nano particles, 2.97g of ethylene glycol dimethacrylate cross-linking agent and 200mg of 2, 2-azobisisobutyronitrile AIBN initiator react for 24 hours at the temperature of 60 ℃ under the protection of nitrogen, after the reaction is finished, the collected product is filtered, and the whole trichloroacetic acid is eluted by using an eluting solution consisting of 10wt% of NaCl and 4wt% of NaOH, and then is soaked and washed by methanol, and is dried to constant weight in vacuum at the temperature of 40 ℃ to obtain the magnetic extractant ME-I.
Example 7
Preparation of magnetic extractant ME-II: according to the method for preparing the magnetic extractant ME-I in example 6 and using the secondary alcohol @ quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + Substitution primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + The magnetic extractant ME-II is prepared.
Example 8
In order to examine the extraction performance of the magnetic extractant ME on haloacetic acid, an extraction experiment is carried out, and the specific experimental method is as follows:
experiment one: extraction experiment of magnetic extractant ME on monochloroacetic acid
Preparing 20mL of perchloroacetic acid solution HAAs-Cl with the concentration of 5 mu mol/mL, adding20mg of magnetic extractant ME-I was extracted with stirring for 1 hour, the magnetic extractant was concentrated with an externally applied magnetic field, and the magnetic extractant was taken out to determine the concentration of HAAs-Cl in the remaining monochloroacetic acid solution, which was designated as C HAAs-Cl -I, from which the extraction quantity E of the magnetic extractant ME-I with respect to monochloroacetic acid is calculated HAAs-Cl -Ⅰ；
Wherein the extraction amount E HAAs-Cl -Ⅰ(µmol/mg)=[(5µmol/mL-C HAAs-Cl -Ⅰ)×20mL]/20mg；
Preparing 20mL of perchloroacetic acid solution HAAs-Cl with the concentration of 5 mu mol/mL, and adding 20mg of magnetic extractant ME-I and 1mg of FeCl 3 The catalyst was extracted for 1h with stirring, the magnetic extractant was enriched with an externally applied magnetic field and was removed, and the concentration of the remaining monochloroacetic acid solution HAAs-Cl, noted C, was determined HAAs-Cl -I-ca, from which the extraction quantity E of monochloroacetic acid by the magnetic extractant ME-I is calculated HAAs-Cl -Ⅰ-ca(µmol/mg)=[(5µmol/mL-C HAAs-Cl -Ⅰ-ca)×20mL]/20mg；
Preparing a 20mL monochloroacetic acid solution HAAs-Cl with the concentration of 5 mu mol/mL, adding 20mg of magnetic extractant ME-II, stirring and extracting for 1h, enriching the magnetic extractant by using an externally applied magnetic field, taking out the magnetic extractant, and determining the concentration of the residual monochloroacetic acid solution HAAs-Cl, wherein the concentration is marked as C HAAs-Cl -II, from which the extraction quantity E of monochloroacetic acid by the magnetic extractant ME-II is calculated HAAs-Cl -Ⅱ(µmol/mg)=[(5µmol/mL-C HAAs-Cl -Ⅱ)×20mL]/20mg；
Preparing 20mL of perchloroacetic acid solution HAAs-Cl with concentration of 5 mu mol/mL, and adding 20mg of magnetic extractant ME-II and 1mg of FeCl 3 The catalyst was extracted for 1h with stirring, the magnetic extractant was enriched with an externally applied magnetic field and was removed, and the concentration of the remaining monochloroacetic acid solution HAAs-Cl, noted C, was determined HAAs-Cl -II-ca, from which the extraction quantity E of monochloroacetic acid by the magnetic extractant ME-II is calculated HAAs-Cl -Ⅱ-ca(µmol/mg)=[(5µmol/mL-C HAAs-Cl -Ⅱ-ca)×20mL]/20mg；
The experimental data of the magnetic extractant ME for the extraction of monochloroacetic acid are shown in table 1 below;
TABLE 1
| Experimental example of extraction | Extraction quantity (mu mol/mg) |
| E HAAs-Cl -Ⅰ | 1.689 |
| E HAAs-Cl -Ⅰ-ca | 2.076 |
| E HAAs-Cl -Ⅱ | 1.621 |
| E HAAs-Cl -Ⅱ-ca | 2.067 |
Experiment II: in the extraction experiment of the magnetic extractant ME on the dichloroacetic acid, the dichloroacetic acid is used for replacing the monochloroacetic acid, and the rest steps are referred to in experiment I;
the extraction experimental data of the magnetic extractant ME on dichloroacetic acid are shown in the following table 2;
TABLE 2
| Experimental example of extraction | Extraction quantity (mu mol/mg) |
| E HAAs-Cl2 -Ⅰ | 1.570 |
| E HAAs-Cl2 -Ⅰ-ca | 2.082 |
| E HAAs-Cl2 -Ⅱ | 1.568 |
| E HAAs-Cl2 -Ⅱ-ca | 2.083 |
Experiment III: for the extraction experiment of the magnetic extractant ME on trichloroacetic acid, trichloroacetic acid is used for replacing monochloroacetic acid, and the rest steps are referred to in experiment I;
the extraction experimental data of the magnetic extractant ME on trichloroacetic acid are shown in table 3 below, from which fig. 5 is plotted;
TABLE 3 Table 3
| Experimental example of extraction | Extraction quantity (mu mol/mg) |
| E HAAs-Cl2 -Ⅰ | 1.542 |
| E HAAs-Cl2 -Ⅰ-ca | 2.076 |
| E HAAs-Cl2 -Ⅱ | 1.514 |
| E HAAs-Cl2 -Ⅱ-ca | 2.079 |
Experiment IV: for the extraction experiment of the magnetic extractant ME on the monobromoacetic acid, the monobromoacetic acid is used for replacing the monochloroacetic acid, and the rest steps are referred to in experiment I;
the experimental data of the extraction of the magnetic extractant ME on the monobromoacetic acid are shown in the following table 4;
TABLE 4 Table 4
| Experimental example of extraction | Extraction quantity (mu mol/mg) |
| E HAAs-Br -Ⅰ | 1.010 |
| E HAAs-Br -Ⅰ-ca | 1.695 |
| E HAAs-Br -Ⅱ | 1.003 |
| E HAAs-Br -Ⅱ-ca | 1.708 |
Experiment five: in the extraction experiment of the magnetic extractant ME on dibromoacetic acid, dibromoacetic acid is used for replacing monochloroacetic acid, and the rest steps are referred to in experiment I;
the extraction experimental data of the magnetic extractant ME on dibromoacetic acid are shown in the following table 5;
TABLE 5
| Experimental example of extraction | Extraction quantity (mu mol/mg) |
| E HAAs-Br2 -Ⅰ | 1.007 |
| E HAAs-Br2 -Ⅰ-ca | 1.653 |
| E HAAs-Br2 -Ⅱ | 1.015 |
| E HAAs-Br2 -Ⅱ-ca | 1.660 |
Example 9
From the extraction experimental data of tables 1 to 5, it can be seen that: both magnetic extractant ME-I and magnetic extractant ME-II can be used to extract haloacetic acid; when haloacetic acid is extracted under the stirring action, the Lewis acid catalyst is added, so that the extraction capacity of the magnetic extractant ME-I and the magnetic extractant ME-II can be remarkably improved;
as can be seen from fig. 5: the extraction capacity of the magnetic extractant ME-I is slightly better than that of the magnetic extractant ME-II only by stirring 3 The catalyst participates in the stirring extraction process of trichloroacetic acid, so that the extraction effect between the catalyst and the trichloroacetic acid is basically equivalent.
Example 10
Solid phase extraction method of haloacetic acid: taking 10.00mL of water quality sample to be measured, and adding the water to be measuredThe mass sample is added with 10mg of magnetic extractant ME and 1mg of FeCl 3 The catalyst is stirred and extracted for 1h, the magnetic extractant ME is enriched by using an external magnetic field, the magnetic extractant ME is taken out, the haloacetic acid is eluted by using eluent (10 wt% NaCl and 4wt% NaOH), the haloacetic acid is dried by nitrogen, and then is redissolved to 100 mu L by using mobile phase (phosphoric acid-triethylamine buffer solution pH=3.2 and methanol), and 10 mu L is taken as the sample injection volume of a liquid phase mass spectrometer;
wherein, magnetic extractant ME selects magnetic extractant ME-I and/or magnetic extractant ME-II.
Claims (9)
1. The method for detecting the water disinfection byproducts is characterized in that the haloacetic acid is extracted by using a magnetic extractant ME, and the specific extraction steps are as follows: adding a magnetic extractant ME and a Lewis acid catalyst into a water quality sample to be measured, stirring and extracting, enriching the magnetic extractant ME by using an external magnetic field, taking out the magnetic extractant ME, eluting haloacetic acid by using an eluent, drying by nitrogen, and re-dissolving by using a mobile phase to be used as a sample sampled by a liquid phase mass spectrometer;
the preparation method of the magnetic extractant ME comprises the following steps:
step S1, preparing a hydroxyl@quaternary ammonium salt functional monomer, wherein the preparation steps are as follows:
s1-1, preparation of trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 The preparation method comprises the following steps: using styrene as raw material, using paraformaldehyde and hydrochloric acid as chloromethylation reagent, under the synergistic catalysis of protonic acid and Lewis acid, making polychloromethylation reaction on aromatic ring of styrene to obtain trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 ；
S1-2 Sulfur functionality Using a thiolating reagent with a trichloromethylated monomer M-Vinyl- (CH) 2 Cl) 3 Nucleophilic substitution reaction of chloromethyl functional group, hydrolysis reaction in alkaline solution, and preparation of trimercapto monomer M-Vinyl- (SH) 3 ；
S1-3 by means of a trimercapto monomer M-Vinyl- (SH) 3 The sulfhydryl functional group of (2) and the epoxy functional group of 2, 3-epoxypropyl trimethyl ammonium chloride undergo a ring-opening reaction to generate a hydroxyl@quaternary ammonium salt functional monomer;
step S2, self-assembling quaternary ammonium positive ions of hydroxyl@quaternary ammonium salt functional monomers and carboxyl anions of haloacetic acid through electrostatic acting force;
step S3, carrying out esterification reaction on hydroxyl functional groups of the hydroxyl@quaternary ammonium salt functional monomer and carboxyl functional groups of the haloacetic acid under the catalysis of Lewis acid to obtain a haloacetic acid template functional monomer M-Vinyl;
step S4, grafting and polymerizing the haloacetic acid template functionalized monomer M-Vinyl to Fe modified by methacryloxy functional groups under the action of an initiator and a crosslinking agent 3 O 4 And eluting the haloacetic acid template from the surface of the magnetic nano particles to prepare the magnetic extractant ME.
2. The method for detecting water disinfection byproducts according to claim 1, wherein the eluent used for the haloacetic acid elution consists of 5-15 wt% of NaCl and 1-5 wt% of NaOH.
3. The method for detecting byproducts of water disinfection according to claim 1, wherein the mobile phase used for the haloacetic acid reconstitution is phosphoric acid-triethylamine buffer solution with ph=3.2 and methanol.
4. The method for detecting byproducts of water disinfection according to claim 1, wherein ZnCl is selected as the Lewis acid in the step S1-1 2 、SnCl 4 、FeCl 3 、AlCl 3 One or a combination of more than one of them.
5. The method for detecting byproducts of water disinfection according to claim 1, wherein the hydroxyl group @ quaternary ammonium salt functional monomer in step S1 comprises: primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + And/or secondary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + 。
6. The method for detecting byproducts of water disinfection according to claim 5, wherein the primary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CH) 2 OH)-N + The preparation method of (2) is as follows: by utilizing the acid catalysis mechanism of mercapto-epoxy reaction, under the action of Lewis acid catalyst, through trimercapto monomer M-Vinyl- (SH) 3 The sulfhydryl functional group of (2) and the epoxy functional group of 2, 3-epoxypropyl trimethyl ammonium chloride undergo a regional ring-opening reaction to generate a primary alcohol@quaternary ammonium salt functional monomer M-Vinyl- (CH) 2 OH)-N + 。
7. The method for detecting byproducts of water disinfection according to claim 6, wherein the Lewis acid catalyst is selected from one or more of boric acid, phenylboric acid, and pentafluorophenylboric acid.
8. The method for detecting byproducts of water disinfection according to claim 5, wherein the secondary alcohol@quaternary ammonium salt functional monomer M-Vinyl- (CHOH) -N + The preparation method of (2) is as follows: by utilizing the base catalysis mechanism of mercapto-epoxy reaction, under the action of organic base catalyst, through trimercapto monomer M-Vinyl- (SH) 3 The sulfhydryl function of (2) and the epoxy function of 2, 3-epoxypropyl trimethyl ammonium chloride occur in accordance with SN 2 Click chemistry reaction of nucleophilic ring opening mechanism to produce secondary alcohol@quaternary ammonium salt functionalized monomer M-Vinyl- (CHOH) -N + 。
9. The method for detecting byproducts of water disinfection according to claim 8, wherein the organic base catalyst is selected from one or more of tetrabutylammonium fluoride, 1,5, 7-triazido bicyclo (4.4.0) dec-5-ene, and 1, 8-bis-dimethylaminonaphthalene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310566378.7A CN116272919B (en) | 2023-05-19 | 2023-05-19 | Method for detecting by-products of water disinfection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310566378.7A CN116272919B (en) | 2023-05-19 | 2023-05-19 | Method for detecting by-products of water disinfection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116272919A CN116272919A (en) | 2023-06-23 |
| CN116272919B true CN116272919B (en) | 2023-07-28 |
Family
ID=86820597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310566378.7A Active CN116272919B (en) | 2023-05-19 | 2023-05-19 | Method for detecting by-products of water disinfection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116272919B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107422053B (en) * | 2017-07-04 | 2020-08-21 | 苏州出入境检验检疫局检验检疫综合技术中心 | Method for detecting trichloroacetic acid in cosmetics by liquid chromatography-mass spectrometry |
| CN108828081B (en) * | 2018-04-17 | 2021-02-05 | 南京大学 | Analysis method for simultaneously detecting nine kinds of haloacetic acids and three kinds of oxyhalides in water |
| CN115236229A (en) * | 2022-07-20 | 2022-10-25 | 苏州大学 | Gas chromatography-mass spectrometry analysis method for haloacetic acid in drinking water |
-
2023
- 2023-05-19 CN CN202310566378.7A patent/CN116272919B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN116272919A (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Torrejos et al. | Liquid-liquid extraction of lithium using lipophilic dibenzo-14-crown-4 ether carboxylic acid in hydrophobic room temperature ionic liquid | |
| Ohto et al. | Selective extraction of silver (I) over palladium (II) with ketonic derivatives of calixarenes from highly concentrated nitric acid | |
| EP2817805B1 (en) | Solid-liquid process for extraction of radionuclides from waste solutions | |
| US20240076195A1 (en) | Task-specific ionic liquids for selective separation and recovery of rare earth elements | |
| JP5619238B1 (en) | Scandium recovery method | |
| CN116272919B (en) | Method for detecting by-products of water disinfection | |
| Xu et al. | A novel N-methylimidazolium-based poly (ionic liquid) to recover trace tetrachloroaurate from aqueous solution based on multiple supramolecular interactions | |
| CN114524948A (en) | 3D supramolecular material with various coordination configurations and preparation method and application thereof | |
| Parker et al. | Interactions of vanadium (IV) with amidoxime ligands: redox reactivity | |
| CN114044844A (en) | Chelate resin and preparation method and application thereof | |
| CN111218562B (en) | Preparation of high-molecular extracting agent and method for efficiently recovering palladium by using high-molecular extracting agent | |
| EP4163009A1 (en) | Cellulose derivative and metal adsorbent containing said cellulose derivative | |
| Huang et al. | Synthesis of a magnetic crown ether ion imprinted polymer material for the selective adsorption of lithium | |
| CN111077196A (en) | Processing method of nano material composite and application of nano material composite in bisphenol A detection | |
| CN114057915B (en) | Dicarbonyl chelate resin and preparation method and application thereof | |
| CN110078630B (en) | Preparation method of ethylenediamine and product thereof | |
| WO2014175771A1 (en) | Method for producing a sorbent for selective recovery of scandium ions | |
| CN113185463A (en) | Ionic liquid compound, preparation method thereof and application of ionic liquid compound as extracting agent | |
| CN111943867A (en) | Dimethylglyoxime polyoxyethylene ether and preparation method and application thereof | |
| CN105384772B (en) | Method for preparing fully-substituted calix [8] arene phosphate derivative | |
| CN112920230B (en) | Metal-based complex containing zinc and molybdate ions and synthesis method thereof | |
| CN117904434A (en) | Palladium ion extractant material and preparation method thereof | |
| CN117447630B (en) | Mercapto resin, and preparation method and application thereof | |
| CN112778239B (en) | Epoxy compound containing column [5] arene and preparation method thereof | |
| CN116425997B (en) | Metal organic frame material, ligand and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |