CN108047361A - A kind of Properties of Magnetic Chelating Resins, its preparation method and its application in combined pollution water body purification - Google Patents
A kind of Properties of Magnetic Chelating Resins, its preparation method and its application in combined pollution water body purification Download PDFInfo
- Publication number
- CN108047361A CN108047361A CN201810006928.9A CN201810006928A CN108047361A CN 108047361 A CN108047361 A CN 108047361A CN 201810006928 A CN201810006928 A CN 201810006928A CN 108047361 A CN108047361 A CN 108047361A
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- Prior art keywords
- magnetic
- properties
- particle
- chelating resins
- reaction
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- 229920001429 chelating resin Polymers 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 43
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000000746 purification Methods 0.000 title claims description 7
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 32
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 239000005416 organic matter Substances 0.000 claims abstract description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 13
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005642 Oleic acid Substances 0.000 claims abstract description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 11
- 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 claims abstract description 10
- 230000005415 magnetization Effects 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 47
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 23
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 230000008961 swelling Effects 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000004098 Tetracycline Substances 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims description 10
- 229960000623 carbamazepine Drugs 0.000 claims description 10
- 229960003405 ciprofloxacin Drugs 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229960002180 tetracycline Drugs 0.000 claims description 10
- 229930101283 tetracycline Natural products 0.000 claims description 10
- 235000019364 tetracycline Nutrition 0.000 claims description 10
- 150000003522 tetracyclines Chemical class 0.000 claims description 10
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- DKYWVDODHFEZIM-UHFFFAOYSA-N ketoprofen Chemical compound OC(=O)C(C)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 DKYWVDODHFEZIM-UHFFFAOYSA-N 0.000 claims description 6
- 229960000991 ketoprofen Drugs 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 239000006249 magnetic particle Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229960003742 phenol Drugs 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 5
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- 239000008273 gelatin Substances 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 claims description 5
- 239000002905 metal composite material Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- -1 methacryloxy Chemical group 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 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 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical class O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 2
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- 239000003921 oil Substances 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- ULYYKJOKMJBFLF-UHFFFAOYSA-N 2-(3-benzoylphenyl)propanoic acid phenol Chemical compound OC(=O)C(C)C1=CC(C(=O)C2=CC=CC=C2)=CC=C1.C1(=CC=CC=C1)O ULYYKJOKMJBFLF-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000001458 anti-acid effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000040710 Chela Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229940069428 antacid Drugs 0.000 description 2
- 239000003159 antacid agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000036571 hydration Effects 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
- C08F2/00—Processes of polymerisation
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- C08F2/16—Aqueous medium
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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Abstract
The present invention is prepared for a kind of novel magnetic high-ratio surface chelating resin, is mainly obtained by following steps：(1) magnetic nano-particle is prepared by coprecipitation, it is surface modified using oleic acid, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane successively；(2) temperature program is strictly controlled, makes the magnetic nano-particle after modification that suspension polymerisation occur with divinylbenzene and methyl acrylate；(3) post-crosslinking is carried out to resin to react with groupization.The Properties of Magnetic Chelating Resins specific saturation magnetization that the present invention develops is high, has both higher specific surface area and group content, can have good removal effect to the combined pollution system that organic matter and heavy metal coexist, have excellent application prospect.
Description
Technical field
The present invention relates to a kind of Properties of Magnetic Chelating Resins and preparation method thereof and it is compound in purifying organic and heavy metal
Application in polluted-water belongs to Properties of Magnetic Chelating Resins and its preparing technical field.
Background technology
Pollutant kind is various in environment water, forms the combined pollution state that multiple pollutant coexists.Wherein, You Jihe
The combined pollution of inorganic substances particularly poisons the complexing of organic matter and heavy metal, is the important problem that current water process faces.
Organic matter and heavy metal can by being coordinated, adsorb or chemical action is combined together, change its form, transportion and transformation and
Bio-toxicity often brings higher ecological risk.
Absorption method is the common efficient depth removal technology that organic matter, heavy metal ion etc. poison pollutant.Resin adsorption
Agent is widely used in a variety of water because its adsorption capacity is big, high mechanical strength, structure is controllable, is easy to the advantages that desorption and regeneration
It handles in engineering.The fast development of magnetic resin and full-mixing type adsorption treatment process in recent years solves usual resins absorption skill
The problem of art investment is big, operating cost is high, further expands its application range.Chelating resin because its selectivity it is strong, for
It is used widely in heavy metal ion adsorbed removal.But the absorption of system coexists for organic matter and heavy metal for it, then shows slightly
Deficiency especially is difficult to effectively remove to organic matter.
CN 201310264731.2 discloses a kind of amido modified magnetic hypercrosslinked polymeric resin material, while has higher
Specific surface area and ion exchange capacity, effectively can synchronously remove all kinds of organic pollutions in water body.But this resinoid is with third
E pioic acid methyl ester (MA) and divinylbenzene (DVB) tend to lead because intersolubility is bad as monomer both in polymerization process
Cause polymerization effect bad；And during trial prepares magnetic material, the magnetic nano-particle amount of introducing is relatively fewer, influences
Final separating property, and nano-particle is easier to dissolve out during use, influences water quality.
CN 201310330339.3 discloses a kind of weak acid modification high-specific surface area magnetic resin, utilizes oleic acid coated magnetic
Nano-particle can enhance the affinity between magnetic nano-particle and oil phase to a certain extent, improve methyl acrylate
(MA) with the polymerization effect of divinylbenzene (DVB).However the improvement of this affinity is limited so that the magnetism of resin is relatively low, and
And in application process, the acid resistance of resin is not high, and magnetic nano-particle easily dissolves out.
The content of the invention
Goal of the invention：The technical problems to be solved by the invention are in view of the deficiencies of the prior art, to provide a kind of magnetic chela
Resin and preparation method thereof, solves that magnetic nano-particle and reaction monomers are difficult to effective integration and resin acid resistance is not strong asks
Topic, while effectively purified using the Properties of Magnetic Chelating Resins for organic matter and heavy-metal composite pollution water body.
In order to solve the above-mentioned technical problem, the invention discloses a kind of preparation method of Properties of Magnetic Chelating Resins, including following
Step：
(a) preparation of magnetic nano-particle：Under the protection of nitrogen by molar ratio be 1:0.4~1:0.6 six hydrations three
Iron chloride and Iron dichloride tetrahydrate are dissolved in deionized water, are warming up to 75~85 DEG C of 30~60min of reaction, and cooling is cleaned；
(b) surface modification of magnetic nano-particle：Under nitrogen protection, magnetic particle prepared by step (a) is added to
In the ammonium hydroxide of 0.16~0.18wt%, oleic acid is added in after being uniformly mixed, is used after being warming up to 75~85 DEG C of 30~60min of reaction
Then it with acetone is mixed and is placed in 25~28wt% ammonium hydroxide by methanol rinse, add in vinyltriethoxysilane in 30
After~50 DEG C of 4~8h of reaction, add in methacryloxypropyl trimethoxy silane and 4~8h, cooling are reacted in 30~50 DEG C
After use methanol rinse；The acetone is the solvent of reaction, and dosage, which ensures to react, fully to be carried out, generally magnetic particles
10~35 times of protonatomic mass.
(c) suspension polymerization：Mix as oil phase using reaction monomers with pore-foaming agent toluene, reaction monomers are diethyl
Alkene benzene and methyl acrylate, mass ratio 1:0.6~1:2, the mass ratio of reaction monomers and pore-foaming agent is 1:0.5~1:2, to oil
The magnetic nano-particle after step (b) is modified and initiator benzoyl peroxide are added in phase, the amount of magnetic nano-particle is oil
The 10~30% of phase quality, the amount of initiator are the 0.5~1% of oil phase quality；Stirring is warming up to 35~45 DEG C, and reaction 30~
After 60min add in water mutually continue to stir, water mutually for containing mass fraction 2~5% gelatin and 5~25% sodium chloride it is water-soluble
Liquid, the water amount of being added to are 4~8 times of oil phase quality；Then with the speed of 3~8 DEG C/min, temperature is risen into 75~85 DEG C of reactions
1~2h, then 90~95 DEG C of 6~12h of reaction are warming up to, after cooling magnetic resin is obtained with methanol rinse；
(d) groupization is reacted：Magnetic resin obtained by previous step is placed in 2~6h of swelling in tetraethylenepentamine solution, tree
Fat and the mass ratio of tetraethylenepentamine are 1:2~1:5, after swelling at 125~140 DEG C stirring and condensing reflux reaction 20~
26h uses methanol rinse after cooling；
(e) post-crosslinking reaction：Magnetic resin obtained by previous step is placed in 1~4h of swelling, resin in 1,2- dichloroethanes
Mass ratio with 1,2- dichloroethanes is 1:5~1:10, swelling later add in anhydrous ferric chloride, in 75~85 DEG C react 6~
10h, the quality of anhydrous ferric chloride are the 15~25% of magnetic resin quality, after reaction cooling methanol rinse, deionization
Water cleans, drying.
Preferably, above-mentioned steps are not the absolute limitations to preparation order, and simply most preferred scheme, excellent as other
Scheme is selected, preparation process is prepared using (a)~(c), (e), the order of (d), and it is unfavorable that the result of the present invention will not be caused
Influence.
In step (b), the mass ratio of the oleic acid and magnetic nano-particle is 1:1~5:1, preferably 1:1.
In step (b), the vinyltriethoxysilane is previously dissolved in acetone, vinyltriethoxysilane and third
The mass ratio of ketone preferably 1:5~1:10, the mass ratio of magnetic nano-particle and vinyltriethoxysilane is 1:2~1:10,
It is preferred that 1:2.
In step (b), the methacryloxypropyl trimethoxy silane is previously dissolved in acetone, methacryl
The mass ratio of oxygroup propyl trimethoxy silicane and acetone preferably 1:5~1:10, magnetic nano-particle and methacryloxy
The mass ratio of propyl trimethoxy silicane is 1:2~1:10, preferably 1:2.
Preferably, in step (c), for the rotating speed of stirring not higher than 100rpm, water will stirring speed after being added to before water is added to
Degree rises to 200~500rpm.
The Properties of Magnetic Chelating Resins being prepared using any one above-mentioned preparation method is also in protection scope of the present invention.
Further, which is 400~900m2/ g, functional group content for 3.25~
6.12mmol/g, specific saturation magnetization are 8.2~22.5emu/g.
Application of the above-mentioned Properties of Magnetic Chelating Resins in containing organic matter and heavy-metal composite pollution water body purification is also in the present invention
Protection domain in.
Further, the organic matter is one kind in tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen and phenol etc.
Or a variety of mixing；The heavy metal is one or more mixing in Cu, Ni, Pb and Cr etc..
The present invention is first by magnetic nano-particle successively through oleic acid, vinyltriethoxysilane and methacryloxy
Propyl trimethoxy silicane carries out surface modification, greatlys improve the affinity between magnetic nano-particle and oil phase, meanwhile, second
The addition of alkenyl triethoxysilane and methacryloxypropyl trimethoxy silane significantly improves the antiacid of magnetic resin
Performance.
Then by the use of divinylbenzene and methyl acrylate as reaction monomers, mixing pore-foaming agent, initiator are mutually carried out with water
Magnetic resin is prepared in suspension polymerisation, then reacts to form ammonium salt through group, most obtains magnetic chela through post-crosslinking reaction afterwards
Resin；Or magnetic resin first passes through post-crosslinking reaction, and Properties of Magnetic Chelating Resins then is obtained by the reaction through group.
Advantageous effect：
1st, the application is successively using oleic acid, vinyltriethoxysilane, methacryloxypropyl trimethoxy silicon
The magnetic nano-particle that alkane prepares coprecipitation is surface modified, and enhances the affine energy between magnetic nano-particle and oil phase
Power improves the specific saturation magnetization of resin, and resin is made to be easy to Magnetic Isolation, while improves the Antacid effectiveness of resin.
2nd, the application uses magnetic nano-particle packaging method, improves and polymer monomer divinylbenzene and acrylic acid first
Affinity between ester improves the yield of resin.
3rd, Properties of Magnetic Chelating Resins prepared by the application not only has higher functional group content, can be to the weight in water body
Metal ion carries out chelating removal, while also has higher specific surface area, can be solved with the organic matter in efficient absorption water body
The problem of chelating resin is ineffective to organic matter removal at present, suitable for the quick of organic matter and heavy-metal composite pollution water body
High-efficient purification.
Description of the drawings
The present invention is done with reference to the accompanying drawings and detailed description and is further illustrated, of the invention is above-mentioned
And/or otherwise advantage will become apparent.
Fig. 1 is the basic structure schematic diagram of Properties of Magnetic Chelating Resins of the present invention.
Fig. 2 is the hysteresis loop figure of the Properties of Magnetic Chelating Resins prepared by embodiment 1.
Fig. 3 is the hysteresis loop figure of Properties of Magnetic Chelating Resins bubble acid after a week prepared by embodiment 1.
Specific embodiment
According to following embodiments, the present invention may be better understood.
Embodiment 1
0.1mol Iron(III) chloride hexahydrates and 0.04mol Iron dichloride tetrahydrates are dissolved in 500mL deionized waters, in nitrogen
75 DEG C of reaction 30min are warming up under the protection of gas, magnetic nano-particle is made, cooling is cleaned；
Obtained 10g magnetic particles are added in the ammonium hydroxide that 200mL concentration is 0.16%, added in after being uniformly mixed
10g oleic acid is modified, and uses methanol rinse after being warming up to 75 DEG C of reaction 30min, then it is mixed with 100g acetone and is placed on
200mL concentration is in 25% ammonium hydroxide, adds in the vinyltriethoxysilane modification that 20g is dissolved in 100g acetone, anti-in 30 DEG C
After answering 4h, add in the methacryloxypropyl trimethoxy silane that 20g is dissolved in 100g acetone and react 4h again in 30 DEG C
Modification, methanol rinse is used after cooling；
By the magnetic nano-particle 14.4g after modification and 20g divinylbenzenes, 12g methyl acrylates, 16g toluene, 0.24g
After benzoyl peroxide mixing, under the rotating speed of 50rpm, 35 DEG C are warming up to, 200mL is added in containing mass fraction after reacting 30min
The water phase of 5% gelatin and 25% sodium chloride, while mixing speed is risen into 200rpm, then with the speed of 3 DEG C/min, by temperature
Degree rises to 75 DEG C of reaction 1h, then is warming up to 90 DEG C of reaction 6h, and magnetic resin is obtained with methanol rinse after cooling；
The tetraethylenepentamine solution swelling 2h of 2 times of resin quality is subsequently placed in, stirs and condenses at 130 DEG C after swelling
Back flow reaction 20h uses methanol rinse after cooling；
Then magnetic resin obtained by previous step is placed in 1, the 2- dichloroethanes of 5 times of resin quality and is swollen 1h, added in
Quality is 15% anhydrous ferric chloride of resin quality, reacts 6h in 75 DEG C, is cleaned simultaneously with methanol rinse, deionized water after reaction
It is dry.
Obtained Properties of Magnetic Chelating Resins specific surface area is 869m2/ g, functional group content are 3.25mmol/g, compare saturation
The intensity of magnetization is 22.5emu/g.0.05g resins is taken to be placed in the combined pollution water body of 100mL organic matters and heavy metal and handle 1h,
Wherein organic pollution is tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen, phenol, and concentration is respectively 0.01mmol/L；Weight
Metal is respectively Cu, Ni, Pb, Cr, and concentration is respectively 0.02mmol/L, and after testing, removal rate is as shown in table 1, magnetism chelating tree
The basic structure of fat is shown in Fig. 1；Prepared Properties of Magnetic Chelating Resins hysteresis loop figure is shown in Fig. 2, it is seen that the ratio saturated magnetization of resin is strong
It spends for 22.5emu/g, there is very strong magnetism, Magneto separate can be effectively performed；By the Properties of Magnetic Chelating Resins of preparation pH be 2
Hydrochloric acid solution impregnate after a week, measure its specific saturation magnetization, the results are shown in Figure 3, the specific saturation magnetization of resin
Only decline 3.19emu/g than the resin (pH=7) without acid treatment, still with stronger magnetism, therefore the chelating resin has
Stronger Antacid effectiveness.
Table 1
| Pollutant | Tetracycline | Ciprofloxacin | Carbamazepine | Ketoprofen | Phenol | Cu | Ni | Pb | Cr |
| Removal rate (%) | 92.4 | 90.5 | 98.2 | 97.6 | 92.1 | 98.7 | 97.2 | 99.6 | 97.3 |
Embodiment 2
0.03mol Iron(III) chloride hexahydrates and 0.018mol Iron dichloride tetrahydrates are dissolved in 500mL deionized waters,
85 DEG C of reaction 60min are warming up under the protection of nitrogen, magnetic nano-particle is made, cooling is cleaned；
Obtained 3g magnetic particles are added in the ammonium hydroxide that 200mL concentration is 0.18%, added in after being uniformly mixed
15g oleic acid is modified, and uses methanol rinse after being warming up to 85 DEG C of reaction 60min, then it is mixed with 100g acetone and is placed on
200mL concentration is in 28% ammonium hydroxide, adds in the vinyltriethoxysilane modification that 30g is dissolved in 300g acetone, anti-in 50 DEG C
After answering 8h, add in the methacryloxypropyl trimethoxy silane that 30g is dissolved in 300g acetone and react 8h again in 50 DEG C
Modification, methanol rinse is used after cooling；
By the magnetic nano-particle 4.8g after modification and 6g divinylbenzenes, 10g methyl acrylates, 32g toluene, 0.48g mistakes
After Benzoyl Oxide mixing, under the rotating speed of 50rpm, 45 DEG C are warming up to, 300mL is added in containing mass fraction 2% after reacting 60min
Gelatin and 5% sodium chloride water phase, while mixing speed is risen into 500rpm, then with the speed of 8 DEG C/min, by temperature liter
To 85 DEG C of reaction 2h, then 95 DEG C of reaction 12h are warming up to, magnetic resin is obtained with methanol rinse after cooling；
The tetraethylenepentamine solution swelling 6h of 5 times of resin quality is subsequently placed in, stirs and condenses at 140 DEG C after swelling
Back flow reaction 26h uses methanol rinse after cooling；
Then magnetic resin obtained by previous step is placed in 1, the 2- dichloroethanes of 10 times of resin quality and is swollen 4h, added in
Quality is 25% anhydrous ferric chloride of resin quality, reacts 10h in 85 DEG C, is cleaned after reaction with methanol rinse, deionized water
It is and dry.
Obtained Properties of Magnetic Chelating Resins specific surface area is 415m2/ g, functional group content are 6.12mmol/g, compare saturation
Magnetic intensity is 8.2emu/g.0.05g resins is taken to be placed in the combined pollution water body of 100mL organic matters and heavy metal, wherein handling
1h, organic pollution is tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen, phenol, and concentration is respectively 0.01mmol/L；With much money
It is respectively Cu, Ni, Pb, Cr to belong to, and concentration is respectively 0.02mmol/L, and after testing, removal rate is as shown in table 2：
Table 2
| Pollutant | Tetracycline | Ciprofloxacin | Carbamazepine | Ketoprofen | Phenol | Cu | Ni | Pb | Cr |
| Removal rate (%) | 87.3 | 82.6 | 90.5 | 88.2 | 85.3 | 97.6 | 98.5 | 99.1 | 95.6 |
Embodiment 3
0.05mol Iron(III) chloride hexahydrates and 0.025mol Iron dichloride tetrahydrates are dissolved in 500mL deionized waters,
80 DEG C of reaction 40min are warming up under the protection of nitrogen, magnetic nano-particle is made, cooling is cleaned；
Obtained 5g magnetic particles are added in the ammonium hydroxide that 200mL concentration is 0.17%, added in after being uniformly mixed
10g oleic acid is modified, and uses methanol rinse after being warming up to 80 DEG C of reaction 40min, then it is mixed with 100g acetone and is placed on
200mL concentration is in 25% ammonium hydroxide, adds in the vinyltriethoxysilane modification that 20g is dissolved in 150g acetone, anti-in 40 DEG C
After answering 6h, add in the methacryloxypropyl trimethoxy silane that 20g is dissolved in 150g acetone and react 6h again in 40 DEG C
Modification, methanol rinse is used after cooling；
By the magnetic nano-particle 6g after modification and 10g divinylbenzenes, 10g methyl acrylates, 20g toluene, 0.4g peroxides
After changing benzoyl mixing, under the rotating speed of 50rpm, 40 DEG C are warming up to, 200mL is added in containing mass fraction 4% after reacting 45min
The water phase of gelatin and 15% sodium chloride, while mixing speed is risen into 300rpm, then with the speed of 5 DEG C/min, by temperature liter
To 80 DEG C of reaction 1h, then 92 DEG C of reaction 8h are warming up to, magnetic resin is obtained with methanol rinse after cooling；
The tetraethylenepentamine solution swelling 4h of 4 times of resin quality is subsequently placed in, stirs and condenses at 125 DEG C after swelling
Back flow reaction for 24 hours, uses methanol rinse after cooling；
Then magnetic resin obtained by previous step is placed in 1, the 2- dichloroethanes of 8 times of resin quality and is swollen 3h, added in
Quality is 20% anhydrous ferric chloride of resin quality, reacts 8h in 80 DEG C, is cleaned simultaneously with methanol rinse, deionized water after reaction
It is dry.
Obtained Properties of Magnetic Chelating Resins specific surface area is 657m2/ g, functional group content are 4.97mmol/g, compare saturation
The intensity of magnetization is 15.7emu/g.0.05g resins is taken to be placed in the combined pollution water body of 100mL organic matters and heavy metal and handle 1h,
Wherein organic pollution is tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen, phenol, and concentration is respectively 0.01mmol/L；Weight
Metal is respectively Cu, Ni, Pb, Cr, and concentration is respectively 0.02mmol/L, and after testing, removal rate is as shown in table 3：
Table 3
| Pollutant | Tetracycline | Ciprofloxacin | Carbamazepine | Ketoprofen | Phenol | Cu | Ni | Pb | Cr |
| Removal rate (%) | 89.5 | 88.3 | 95.5 | 93.3 | 90.2 | 97.1 | 96.7 | 99.2 | 95.4 |
Embodiment 4
Magnetic resin preparation method by acquired magnetic resin with embodiment 1, being then placed in the 1,2- of 5 times of resin quality
1h is swollen in dichloroethanes, addition quality is 15% anhydrous ferric chloride of resin quality, reacts 6h in 75 DEG C, uses first after reaction
Alcohol rinses；
The tetraethylenepentamine solution swelling 2h of 2 times of resin quality is subsequently placed in, stirs and condenses at 130 DEG C after swelling
Back flow reaction 20h is cleaned and dried with methanol rinse, deionized water after cooling.
Obtained Properties of Magnetic Chelating Resins specific surface area is 725m2/ g, functional group content are 3.35mmol/g, compare saturation
The intensity of magnetization is 18.6emu/g.0.05g resins is taken to be placed in the combined pollution water body of 100mL organic matters and heavy metal and handle 1h,
Wherein organic pollution is tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen, phenol, and concentration is respectively 0.01mmol/L；Weight
Metal is respectively Cu, Ni, Pb, Cr, and concentration is respectively 0.02mmol/L, and after testing, removal rate is as shown in table 4：
Table 4
| Pollutant | Tetracycline | Ciprofloxacin | Carbamazepine | Ketoprofen | Phenol | Cu | Ni | Pb | Cr |
| Removal rate (%) | 90.5 | 88.1 | 96.5 | 95.6 | 90.4 | 97.6 | 98.3 | 98.1 | 96.7 |
The present invention provides a kind of Properties of Magnetic Chelating Resins, its preparation method and its applications in combined pollution water body purification
Thinking and method, implement that there are many method and the approach of the technical solution, the above is only being preferably implemented for the present invention
Mode, it is noted that for those skilled in the art, without departing from the principle of the present invention, also
Several improvements and modifications can be made, these improvements and modifications also should be regarded as protection scope of the present invention.It is unknown in the present embodiment
The available prior art of true each component is realized.
Claims (10)
1. a kind of preparation method of Properties of Magnetic Chelating Resins, which is characterized in that comprise the following steps：
(a) preparation of magnetic nano-particle：Under the protection of nitrogen by molar ratio be 1:0.4~1:0.6 six trichloride hydrates
Iron and Iron dichloride tetrahydrate are dissolved in deionized water, are warming up to 75~85 DEG C of 30~60min of reaction, and cooling is cleaned；
(b) surface modification of magnetic nano-particle：Under nitrogen protection, magnetic particle prepared by step (a) is added to 0.16~
In the ammonium hydroxide of 0.18wt%, oleic acid is added in after being uniformly mixed, is floated after being warming up to 75~85 DEG C of 30~60min of reaction with methanol
It washes, then it with acetone is mixed and is placed in 25~28wt% ammonium hydroxide, add in vinyltriethoxysilane in 30~50 DEG C
After reacting 4~8h, add in methacryloxypropyl trimethoxy silane and react 4~8h in 30~50 DEG C, first is used after cooling
Alcohol rinses；
(c) suspension polymerization：Mix as oil phase using reaction monomers with pore-foaming agent toluene, reaction monomers are divinylbenzene
And methyl acrylate, mass ratio 1:0.6~1:2, the mass ratio of reaction monomers and pore-foaming agent is 1:0.5~1:2, into oil phase
The magnetic nano-particle after step (b) is modified and initiator benzoyl peroxide are added in, the amount of magnetic nano-particle is oil phase matter
The 10~30% of amount, the amount of initiator are the 0.5~1% of oil phase quality；Stirring is warming up to 35~45 DEG C, reacts 30~60min
It adds in water afterwards mutually to continue to stir, water is mutually gelatin and the aqueous solution of 5~25% sodium chloride containing mass fraction 2~5%, water phase
Addition is 4~8 times of oil phase quality；Then with the speed of 3~8 DEG C/min, temperature is risen into 75~85 DEG C of 1~2h of reaction,
90~95 DEG C of 6~12h of reaction are warming up to again, and magnetic resin is obtained with methanol rinse after cooling；
(d) groupization is reacted：Magnetic resin obtained by previous step is placed in tetraethylenepentamine solution 2~6h of swelling, resin with
The mass ratio of tetraethylenepentamine is 1:2~1:5, simultaneously condensing reflux reacts 20~26h for stirring at 125~140 DEG C after swelling,
Methanol rinse is used after cooling；
(e) post-crosslinking reaction：Magnetic resin obtained by previous step is placed in 1,2- dichloroethanes and is swollen 1~4h, resin and 1,
The mass ratio of 2- dichloroethanes is 1:5~1:10, swelling adds in anhydrous ferric chloride later, reacts 6~10h, nothing in 75~85 DEG C
The quality of water iron chloride is the 15~25% of magnetic resin quality, after reaction cooling methanol rinse, deionized water cleaning,
Drying.
2. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1, which is characterized in that using step (a)~
(c), prepared by (e), the order of (d).
3. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1 or 2, which is characterized in that in step (b),
The mass ratio of the oleic acid and magnetic nano-particle is 1:1~5:1.
4. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1 or 2, which is characterized in that in step (b),
The vinyltriethoxysilane is previously dissolved in acetone, the mass ratio of magnetic nano-particle and vinyltriethoxysilane
For 1:2~1:10.
5. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1 or 2, which is characterized in that in step (b),
The methacryloxypropyl trimethoxy silane is previously dissolved in acetone, magnetic nano-particle and methacryloxy
The mass ratio of propyl trimethoxy silicane is 1:2~1:10.
6. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1 or 2, which is characterized in that in step (c),
The rotating speed of stirring is not higher than 100rpm before water is added to, and mixing speed is risen to 200~500rpm by water after being added to.
7. the Properties of Magnetic Chelating Resins that any one preparation method is prepared in claim 1~6.
8. Properties of Magnetic Chelating Resins according to claim 7, which is characterized in that Properties of Magnetic Chelating Resins specific surface area for 400~
900m2/ g, functional group content are 3.25~6.12mmol/g, and specific saturation magnetization is 8.2~22.5emu/g.
9. Properties of Magnetic Chelating Resins described in claim 7 is containing the application in organic matter and heavy-metal composite pollution water body purification.
10. Properties of Magnetic Chelating Resins according to claim 9 is in containing organic matter and heavy-metal composite pollution water body purification
Using, which is characterized in that the organic matter is one kind or more in tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen and phenol
The mixing of kind；The heavy metal is one or more mixing in Cu, Ni, Pb and Cr.
Priority Applications (1)
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| CN112876598A (en) * | 2021-03-04 | 2021-06-01 | 中国科学院合肥物质科学研究院 | Preparation method of multi-response and anisotropic magnetic hydrogel |
| CN114832797A (en) * | 2022-06-06 | 2022-08-02 | 哈尔滨工业大学 | Lanthanum modified magnetic resin containing two types of quaternary ammonium sites for efficiently adsorbing phosphorus, preparation method thereof and high-density circulating reflux device |
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| CN114832797A (en) * | 2022-06-06 | 2022-08-02 | 哈尔滨工业大学 | Lanthanum modified magnetic resin containing two types of quaternary ammonium sites for efficiently adsorbing phosphorus, preparation method thereof and high-density circulating reflux device |
| CN114832797B (en) * | 2022-06-06 | 2022-11-11 | 哈尔滨工业大学 | Lanthanum modified magnetic resin containing two types of quaternary ammonium sites for efficiently adsorbing phosphorus, preparation method thereof and high-density circulating reflux device |
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