CN111013554A - Composite macroporous adsorption resin for removing perfluorinated compounds in water - Google Patents
Composite macroporous adsorption resin for removing perfluorinated compounds in water Download PDFInfo
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- CN111013554A CN111013554A CN201911392954.0A CN201911392954A CN111013554A CN 111013554 A CN111013554 A CN 111013554A CN 201911392954 A CN201911392954 A CN 201911392954A CN 111013554 A CN111013554 A CN 111013554A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 217
- 239000011347 resin Substances 0.000 title claims abstract description 201
- 229920005989 resin Polymers 0.000 title claims abstract description 201
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000009826 distribution Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 148
- 238000005406 washing Methods 0.000 claims description 89
- 238000010438 heat treatment Methods 0.000 claims description 66
- 239000008367 deionised water Substances 0.000 claims description 60
- 229910021641 deionized water Inorganic materials 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- 238000005303 weighing Methods 0.000 claims description 47
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 42
- 238000001914 filtration Methods 0.000 claims description 38
- 238000002791 soaking Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 22
- 239000012046 mixed solvent Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 18
- 230000008961 swelling Effects 0.000 claims description 18
- 238000006735 epoxidation reaction Methods 0.000 claims description 17
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 12
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 12
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005576 amination reaction Methods 0.000 claims description 11
- 238000010907 mechanical stirring Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 9
- 229960002887 deanol Drugs 0.000 claims description 9
- 239000012972 dimethylethanolamine Substances 0.000 claims description 9
- 150000004967 organic peroxy acids Chemical class 0.000 claims description 9
- 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 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229920001447 polyvinyl benzene Polymers 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=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-N 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000805 composite resin Substances 0.000 claims description 3
- 238000011156 evaluation Methods 0.000 claims description 3
- 239000012434 nucleophilic reagent Substances 0.000 claims description 3
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 claims description 2
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 10
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000002156 adsorbate Substances 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 14
- 238000007306 functionalization reaction Methods 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 14
- 150000002118 epoxides Chemical group 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 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 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- WPDDXKNWUVLZMQ-UHFFFAOYSA-M potassium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [K+].[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 WPDDXKNWUVLZMQ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a composite adsorption resin for removing perfluorinated compounds in water. By introducing functional group modified macroporous adsorption resin, perfluorinated compounds in water are adsorbed based on hydrophobic-charge synergistic effect, so that adsorption capacity and efficiency are improved. The invention epoxidizes the residual double bonds in the skeleton molecule, then carries out ring opening on the skeleton molecule, grafts amino functional groups, and utilizes the charge effect to improve the adsorption effect of the resin on adsorbates. The composite adsorption resin with proper microporous structure, narrow particle size distribution, uniform pore diameter, high specific surface area and specific functional groups is finally obtained, and the screening capacity and adsorption rate of perfluorinated compounds in water are effectively improved.
Description
Technical Field
The invention relates to a composite macroporous adsorption resin for removing perfluorinated compounds in water, in particular to a composite macroporous adsorption resin for removing perfluorinated compounds in water as well as a preparation method and application thereof, belonging to the field of functional polymer materials and environmental protection.
Background
Perfluorooctanesulfonate (Perluorooctane Sulfonate) is used as a final degradation product of a perfluorinated compound, and the structure of the perfluorooctanesulfonate contains a plurality of groups such as carbon fluorine long chains, sulfonic acid and carboxylic acid, so that the perfluorooctanesulfonate has the characteristics of hydrophobicity and oleophobicity. Because of the strong polarity of the C-F bond, PFOS is one of the most recalcitrant organic pollutants. Because of the environmental and human harm of PFOS, the production of related products has been started to be stopped on a global basis.
Traditional materials such as cotton, cellulose, nylon and reverse osmosis membranes can be used for removing perfluorinated compounds, for example, patents CN102489260B, CN102500338B, CN105776404A and CN103408103A describe the application methods of the above materials respectively, which have certain popularization possibilities, but the removal efficiency is low or the industrial application is less due to the cost problem. In addition, some novel treatment methods such as light radiation, photocatalysis, molecular imprinting, induced electrochemistry and the like are mentioned in patents CN104193056B, CN108264127A and CN105001371B to degrade trace perfluorinated compounds in water, but due to harsh conditions, difficult operation, high energy consumption and the like, the practical application cannot be popularized in a large scale.
According to the molecular characteristics of PFOS, the anion exchange resin and the activated carbon material with proper pore diameter can effectively remove trace pollutants in water. The application of ion exchange resins, particularly quaternary amine type anion resins containing more than C8, in water treatment is limited as detailed in patent publication No. CN101605728B, and treatment efficiency is limited in application due to high cost and low exchange capacity of ion exchange resins; activated carbon (granules or powder) is used as the most commonly used filtering and adsorbing material in patents CN106732379A, CN108144572A for removing perfluorooctanoic acid.
Therefore, the prior art for removing perfluorinated compounds in water still lacks of an adsorbent which has low cost, simple operation and high treatment efficiency.
Disclosure of Invention
The invention focuses on the preparation of macroporous adsorption resin with large adsorption capacity, easy elution and long service cycle, starts with the design of a high molecular structure, selects common divinylbenzene as a comonomer and a cross-linking agent, prepares the macroporous adsorption resin with a proper pore structure by adjusting the proportion of a pore-forming agent, epoxidizes residual dangling double bonds in the resin by organic peroxyacid, and then utilizes an aminated nucleophilic reagent to open rings of epoxy groups and graft amino functional groups to prepare the composite resin taking hydrophobic effect as the main consideration and charge effect. The resin product has reasonable microstructure, such as specific surface area, aperture and particle size distribution, and is grafted with groups having strong charge function on perfluoroacids and perfluorosulfonate, so that the resin can effectively remove perfluorooctanoic acid (or salt) pollutants in water.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is divided into three steps: preparing a polystyrene macroporous adsorption resin base sphere, epoxidizing residual suspended double bonds on the base sphere to obtain a resin intermediate, and functionalizing epoxy groups on the resin intermediate.
The specific scheme comprises the following steps:
the method comprises the following steps: preparation of polystyrene macroporous adsorption resin base ball
Styrene, divinylbenzene or polyvinyl benzene are taken as monomers, a pore-foaming agent is added, and the macroporous adsorption resin base ball is prepared by suspension polymerization, and is dried for standby after the pore-foaming agent is removed;
step two: epoxidation of dangling double bonds
Fully swelling the resin-based spheres obtained in the step (1), epoxidizing the dangling double bonds which do not participate in the suspension polymerization reaction in molecular chains by using organic peroxyacid, and washing away the solvent and excessive reactants to obtain a resin intermediate;
step three: functionalization of epoxide groups
And (3) after the resin intermediate in the step (2) is fully swelled, replacing the solvent with water, carrying out ring-opening functionalization reaction on an epoxy group by using an amination nucleophilic reagent in a mixed solvent of water and dioxane, and washing away the solvent to obtain the macroporous adsorption resin grafted with the amino functional group.
More specifically, weighing the resin-based spheres (dried) prepared in the step (1) in a reactor, adding a solvent to ensure that the resin is fully swelled, adding organic peroxy acid into the reactor to react at a low temperature of 0-5 ℃, heating to room temperature after the reaction is finished, soaking and cleaning with ethanol, washing with deionized water, and filtering to obtain a product, thereby obtaining a resin intermediate. Then taking the resin intermediate obtained in the step (2), soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water or pure water, and adding a mixed solvent; mechanically stirring for 0.5-1 hour, adding an amination reagent, heating to 60-75 ℃, and reacting at constant temperature for 24-30 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
In the step (1), the polyvinyl benzene monomer can be one or a mixture of more of styrene, divinylbenzene and divinyl xylene; the pore-forming agent can be one or a mixture of more of toluene, gasoline, methylcyclohexane and n-butanol; the mass ratio of the pore-foaming agent to the polyvinyl benzene monomer is 1-1.4: 1.
In the step (2), the solvent can be one or a mixture of more of acetone, dichloroethane, toluene and xylene, and the mass ratio of the solvent to the resin-based spheres (dried) is 4-6.5: 1; the organic peroxy acid is one or a mixture of more of m-chloroperoxybenzoic acid, peroxyacetic acid, peroxybenzoic acid and trifluoro peroxyacetic acid, and the mass ratio of the organic peroxy acid to the resin-based spheres (dried) is 0.45-0.65: 1.
In the step (3), the mixed solvent is dioxane and water, the mass ratio of the dioxane to the water is 0.5-1:1, and the mass ratio of the mixed solvent to the resin intermediate is 2-3: 1; the amination reagent is one or more of dimethylamine, dimethylethanolamine, trimethylamine, tri-n-butylamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine, and the mass ratio of the amination reagent to the resin intermediate (dry weight) is 0.25-0.5: 1.
The invention provides a preparation method of composite adsorption resin. The resin main body is macroporous adsorption resin, and has a charge function through a grafting functional group, so that the adsorption efficiency is greatly improved, the resin regeneration can be realized through a conventional treatment method, the service life is long, the industrial application cost can be effectively saved, and the method is suitable for removing the perfluorinated substances in sewage and drinking water with large scale and high treatment capacity. The invention can effectively remove the perfluorooctanoic acid (or salt) contained in the water, and the content of perfluorochemicals in the treated water is lower than 70 ng/L. The method has the advantages of simple material synthesis process, no secondary pollution, easy amplification and large-scale product application, and effectively overcomes the defects of other various methods for removing the perfluorooctanoic acid.
Detailed Description
Example one
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 45 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, and slowly adding the oil phase; adjusting the stirring speed to ensure that the size of oil droplets is distributed in 45-20 meshes; heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one (1) into a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 40 g of dioxane and 60 g of water are added; mechanically stirring for 0.5 hour, adding 20 g of dimethylamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Example two
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
step one, suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, and slowly adding the oil phase; adjusting the stirring speed to ensure that the size of oil droplets is distributed in 45-20 meshes; heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and keeping the reaction for 24 hours under mechanical stirring to finish the reaction; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
EXAMPLE III
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, and slowly adding the oil phase; adjusting the stirring speed to ensure that the size of oil droplets is distributed in 45-20 meshes; heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 56 g of dioxane and 84 g of water are contained; mechanically stirring for 0.5 hour, adding 26 g of trimethylamine, raising the temperature, and keeping the constant temperature of 65 ℃ for reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Example four
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, and then washing residual ethanol in the resin with a large amount of deionized water; drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 15 g of diethylenetriamine, raising the temperature, and keeping the constant temperature of 65 ℃ for reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
EXAMPLE five
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, and slowly adding the oil phase; adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 40 g of dioxane and 60 g of water are added; mechanically stirring for 0.5 hour, adding 16 g of triethylene tetramine, raising the temperature, and keeping the temperature of 65 ℃ for constant-temperature reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
EXAMPLE six
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and stopping the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 40 g of dioxane and 60 g of water are added; mechanically stirring for 0.5 hour, adding 16.5 g of tetraethylenepentamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
EXAMPLE seven
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 40 g of dioxane and 60 g of water are added; mechanically stirring for 0.5 hour, adding 17 g of tri-n-butylamine, raising the temperature, keeping the temperature at 65 ℃ and reacting for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Example eight
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 62 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Comparative example 1
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
comparative example No. two
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 45 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and stopping the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: macroporous resin post-crosslinking reaction:
accurately weighing the dry resin-based spheres prepared in the step one in a reactor, adding 800 g of dichloroethane, stirring and swelling for 10 hours at room temperature to ensure that the spheres are fully swelled, cooling to 0-5 ℃ by adopting an ice salt bath, adding 20 g of ferric chloride in batches, keeping the reaction for 30 minutes by adopting the ice salt bath, reacting for 45 minutes at room temperature, heating to 80 ℃, reacting for 10 hours, and finishing the reaction. And soaking and cleaning the resin by using acetone, washing the resin by using deionized water, washing the resin by using ethanol and the deionized water respectively, and filtering to obtain a product.
Comparative example No. three
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
accurately weighing 500 g of deionized water, 4 g of polyvinyl alcohol and 5 g of sodium chloride in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 140 g of toluene, 70 g of gasoline and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Comparative example No. four
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 0.5 g of azobisisobutyronitrile, and the components are fully and uniformly mixed;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Comparative example five
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of methylcyclohexane and 0.5 g of azobisisobutyronitrile, and the components are fully and uniformly mixed;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and stopping the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and mechanically stirring to react for 24 hours; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Comparative example six
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of methylcyclohexane and 0.5 g of azobisisobutyronitrile, and the components are fully and uniformly mixed;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and stopping the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 36 g of peroxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and mechanically stirring to keep reacting for 24 hours to finish the reaction; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Example-evaluation test:
evaluation of Perfluorooctanoic acid (salt) adsorption Performance in Water
Respectively and accurately weighing 0.1 g of eight different resins in the examples and four different resins in the comparative examples, placing the eight resins in a 125 ml polyethylene terephthalate plastic bottle, respectively adding 100 ml of 10ug/L perfluorooctanoic acid and potassium perfluorooctanoate sulfonate solution, placing the mixture in a shaking table, carrying out vibration for 100 hours at 25 ℃ and 150rpm, after the vibration is finished, taking 2 ml of the solution, carrying out high-speed centrifugation, and testing a sample by using LC-MS/MS (liquid chromatography-mass spectrometry/mass spectrometry), wherein relevant results are shown in the table. It can be known from the table that the composite resin which mainly takes the hydrophobic effect as the main part and takes the charge effect as well is prepared by suspending double bond epoxidation and then utilizing an amination reagent to carry out ring opening and grafting amino functional groups, and the removal effect of trace perfluorooctanoic acid (salt) in water is the best and reaches more than 99.3 percent.
Perfluorooctanoic acid (or salt) removing effect of resin prepared by different methods
Claims (18)
1. A composite macroporous adsorption resin for removing perfluorinated compounds in water is characterized in that: the resin has amino functional groups as follows: (R1R2) NH-, (R1R2R3) N-, (R1) NH2-, wherein R1 and R2 are the same or different straight chain or branched chain aliphatic hydrocarbons, R3 is C6 or lower hydrocarbons, the particle size distribution is 0.4-0.85mm, the specific surface area is not less than 500-550 m-2(ii)/g, average micropore diameter of 3-5 nm.
2. The composite macroporous absorption resin for removing the perfluorinated compounds in the water as claimed in claim 1, wherein the preparation process comprises the following steps:
preparing a polystyrene macroporous adsorption resin base ball, performing suspension double bond epoxidation, and performing ring-opening amination reaction on an epoxy group.
3. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 2, comprising the following steps:
(1) preparing a polystyrene macroporous adsorption resin base sphere, taking styrene, divinylbenzene or polyvinyl benzene as monomers, adding a pore-foaming agent, performing suspension polymerization to obtain the macroporous adsorption resin base sphere, removing the pore-foaming agent, and drying for later use;
(2) performing epoxidation on the dangling double bonds, fully swelling the resin-based spheres (dried) obtained in the step (1), performing epoxidation on the dangling double bonds which do not participate in suspension polymerization reaction in molecular chains by using organic peroxyacid, and washing off a solvent and excessive reactants to obtain a resin intermediate;
(3) and (3) performing ring-opening amination reaction on an epoxy group, fully swelling the resin intermediate obtained in the step (2), performing ring-opening reaction on the epoxy group by using an amination nucleophilic reagent, and washing away the solvent to obtain the macroporous adsorption resin grafted with an amino functional group.
4. The method for preparing the composite macroporous absorption resin for removing the perfluorinated compounds in the water as claimed in claim 3, wherein in the step (1), the polyvinyl benzene monomer can be one or a mixture of styrene, divinylbenzene and divinylxylene; the pore-forming agent can be one or a mixture of more of toluene, gasoline, methylcyclohexane and n-butanol.
5. The method as claimed in claim 4, wherein in the step (1), the mass ratio of the pore-forming agent to the polyvinyl benzene monomer is 1-1.5: 1.
6. The method for preparing a composite macroporous adsorbent resin for removing perfluorinated compounds in water as claimed in claim 4, wherein divinylbenzene is removed polymerization inhibitor and has an isotactic ratio of not less than 80%.
7. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 3, wherein the step (2) comprises the following steps:
accurately weighing the resin-based spheres (dried) prepared in the step (1) into a reactor, adding a solvent to ensure that the resin is fully swelled, adding organic peroxy acid into the reactor to react at a low temperature of 0-5 ℃, heating to room temperature after the reaction is finished, soaking and cleaning with ethanol, washing with deionized water, and filtering out a product to obtain a resin intermediate.
8. The method for preparing composite macroporous adsorbent resin for removing perfluorinated compounds in water as claimed in claim 7, wherein the solvent in step (2) is one or more selected from acetone, dichloroethane, toluene and xylene.
9. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 8, wherein the mass ratio of the solvent to the resin-based spheres (dry) in the step (2) is 4-6.5: 1.
10. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 7, wherein the organic peroxyacid in step (2) is one or more of m-chloroperoxybenzoic acid, peroxyacetic acid, peroxybenzoic acid and trifluoroperoxyacetic acid.
11. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 10, wherein the mass ratio of the organic peroxyacid to the resin-based spheres (dry) in the step (2) is 0.45-0.65: 1.
12. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 3, wherein the step (3) comprises the following steps:
taking the resin intermediate obtained in the step (2), soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water or pure water, and adding a mixed solvent; mechanically stirring for 0.5-1 hour, adding an amination reagent, heating to 60-75 ℃, and reacting at constant temperature for 24-30 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
13. The method as claimed in claim 12, wherein the mixed solvent in step (3) is dioxane and water at a mass ratio of 0.5-1: 1.
14. The preparation method of composite macroporous adsorbent resin for removing perfluorinated compounds in water as claimed in claim 12, wherein in step (3), the mass ratio of the mixed solvent to the resin intermediate is 2-3: 1.
15. The method for preparing the composite macroporous adsorbent resin for removing the perfluorinated compounds in water according to claim 12, wherein in the step (3), the amination reagent is one or more of dimethylamine, dimethylethanolamine, trimethylamine, tri-n-butylamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
16. The method for preparing composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 15, wherein in the step (3), the mass ratio of the amination reagent to the resin intermediate (dry weight) is 0.25-0.5: 1.
17. The composite macroporous adsorbent resin for removing perfluorinated compounds in water as claimed in claim 1, wherein the content of perfluorinated compounds in the treated water is less than 70 ng/L.
18. The preparation method of the composite macroporous absorption resin for removing the perfluorinated compounds in the water according to claim 2 is characterized by comprising the following steps,
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing; standing the water phase for 20 minutes, slowly adding the oil phase, and adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes; heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, terminating the reaction, and removing the pore-foaming agent to obtain a resin-based ball; after drying, accurately weighing 80 g of resin-based balls (dry) in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, adding 64 g of m-chloroperoxybenzoic acid in the reactor, controlling the reaction temperature to be kept at 5 ℃, reacting for 24 hours under mechanical stirring, filtering out liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and cleaning with ethanol, washing with deionized water, and filtering out a product; taking 50 g of the obtained resin intermediate, swelling the resin intermediate by using ethanol, adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are mechanically stirred for 0.5 hour, adding 40 g of dimethylethanolamine, heating to 65 ℃, reacting at a constant temperature for 24 hours, filtering out the solution, and respectively washing by using pure water, ethanol and pure water to obtain the composite macroporous adsorption resin, wherein the particle size is distributed between 0.4 and 0.8mm, and the specific surface area is not less than 500-550m2(ii)/g, average micropore diameter 3-5 nm;
the composite resin containing amino functional groups can be prepared by the method, PFOA and PFOS are respectively reduced to 0.027 and 0.025ug/L from 10ug/L of inlet concentration through the adsorption evaluation of perfluorinated compounds in water, the clearance rate is as high as 99.73 percent and 99.65 percent, and the final content of the perfluorinated compounds is lower than 70 ng/L.
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