CN107349916A - A kind of preparation method of magnetic polymer adsorbent for heavy metal - Google Patents
A kind of preparation method of magnetic polymer adsorbent for heavy metal Download PDFInfo
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- CN107349916A CN107349916A CN201710589988.3A CN201710589988A CN107349916A CN 107349916 A CN107349916 A CN 107349916A CN 201710589988 A CN201710589988 A CN 201710589988A CN 107349916 A CN107349916 A CN 107349916A
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- heavy metal
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- deionized water
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 87
- 239000003463 adsorbent Substances 0.000 title claims abstract description 49
- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 42
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 15
- 238000004064 recycling Methods 0.000 claims abstract description 12
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical class CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000005389 magnetism Effects 0.000 claims abstract description 8
- 230000005415 magnetization Effects 0.000 claims abstract description 8
- 230000005408 paramagnetism Effects 0.000 claims abstract description 8
- 230000004043 responsiveness Effects 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 74
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 150000002500 ions Chemical class 0.000 claims description 42
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000010792 warming Methods 0.000 claims description 27
- 229910021529 ammonia Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000003643 water by type Substances 0.000 claims description 21
- -1 chloropropyl Chemical group 0.000 claims description 19
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000006249 magnetic particle Substances 0.000 claims description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 238000002955 isolation Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000012966 redox initiator Substances 0.000 claims description 6
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical class OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 4
- 241000549556 Nanos Species 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DRNNATGSBCVJBN-UHFFFAOYSA-N 2-amino-2-methylpropane-1-sulfonic acid Chemical compound CC(C)(N)CS(O)(=O)=O DRNNATGSBCVJBN-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to a kind of preparation method of magnetic polymer adsorbent for heavy metal,Magnetic nano-particle is prepared using improvement chemical coprecipitation,Then surface modification is carried out to it with γ r-chloropropyl trimethoxyl silanes and polyethyleneimine respectively,Obtain polyethyleneimine-modified magnetic nano-particle,Finally polyethyleneimine-modified magnetic nano-particle and functional monomer are copolymerized,Prepare the magnetic polymer adsorbent for heavy metal with multi-layer cross-linked structure and a variety of adsorption groups,Saturation magnetization is 3.5~15.5 emu/g,Remanent magnetism and coercivity go to zero,With paramagnetism and magnetic responsiveness,It is 100~1000mg/L heavy metal ion aqueous solution for initial concentration,Heavy metal ion adsorbed capacity reaches 35~450mg/g,50~100min reaches adsorption equilibrium,Heavy metal ion adsorbed capacity after recycling utilization 5 times exceedes the 85% of first time adsorption capacity,It can be widely applied to heavy metal ion adsorbed separation and heavy metal ion pollution control etc..
Description
First, technical field
The present invention relates to a kind of preparation method of magnetic polymer adsorbent for heavy metal, magnetic prepared by the present invention is gathered
Compound adsorbent for heavy metal is applied to the adsorbing separation of heavy metal ion, can be widely applied to heavy metal ion adsorbed, again
Separation of metal ions purification and heavy metal ion environmental pollution improvement etc..
2nd, background technology
With the raising of global industry degree, environmental pollution is on the rise, and wherein water pollution has had a strong impact on people's
Production and living, industrial wastewater are the main source of heavy metal pollution of water body, many industrial process, such as plating, process hides, mining, steel-making,
Dyeing etc., can produce the largely waste water containing heavy metal ion, such as Cd2+、Cu2+、Pb2+、Ni2+、As3+、Hg2+、Cr3+、Co2+And Co3+
Deng by heavy metal can not be degraded by biology, after the industrial wastewater of heavy metal ion enters water body environment, aquatic life can be caused
Thing is poisoned, and is enriched with by food chain in human body, threatens the health of human body, therefore heavy metal is excessive rich in food chain
Rally causes very big harm to natural environment and health.The improvement of heavy metal ion-containing waste water is always of concern
Emphasis and difficult point, the method for handling effluent containing heavy metal ions is a lot, and advantage and disadvantage are individually present, and wherein chemical Treatment plating contains zinc
Waste water has the advantages of small investment, treatment technology are easily grasped, and shortcoming is consumption chemical materials, and caused sludge is not easy to discharge；From
Sub- exchange process treating capacity is big, but resin vulnerable to pollution, and operating cost is high；Though absorption method adsorption capacity is big, sorbing material uses
Short life, it must regenerate, operating cost is high.Therefore, a kind of efficient heavy ion removing is being explored and studied to domestic and foreign scholars all
Method.Result of study in recent years shows the exploitation and use of cost effective chemical treatment medicament, is to solve heavy metal wastewater thereby dirt
The good approach of dye problem.
Traditional adsorbent such as ion exchange resin, polymeric adsorbent, carbonaceous class adsorbent and natural mesoporous mineral material
Deng can only be not only time-consuming by centrifuging, filtering, the conventional method separation such as precipitate after, these sorbing materials absorption heavy metal ion
Laborious and not energy-conserving and environment-protective, the structure of destructible sorbing material, the regeneration for sorbing material bring influence.In recent years
Come, the appearance of nano material and nanometer technology has been greatly facilitated the progress and development of heavy mental treatment technology, magnetic Nano
The advantages that material is because of its own distinctive bigger serface, abundant active site and high magnetic is shown in heavy metals removal field
Huge application potential.Magnetic nanometer adsorbent can be with the heavy metal contaminants in adsorbed water body, after the completion of absorption, in outside magnetic
By Magnetic Isolation in the presence of, the fast and effective separation of adsorbent and mother liquor is realized, and cost is low, it is simple to operate, compared with
Solve the problems, such as that common adsorbents separation of solid and liquid is difficult and recovery separation is difficult well.
He etc. is by the way that using hollow cenosphere as core, magnetic material is that shell prepares the magnetic composite with core shell structure, right
The clearance of heavy metals lead ion can be up to 99.7%.Guan Xiaohui etc. uses self-control pellicle Hydrolyze method to prepare with regular spherical
Magnetic Fe_3O_4 nano-particle based on structure, heavy metal ion Pb2+、Cu2+And Cr6+Adsorbed, obtained preferably
Adsorption effect.The magnetic Fe_3O_4 nano-particle that Chai Duoli etc. is prepared using hydro-thermal method, reaches to the clearance of pentavalent arsenic ion in water
90%.Behzad has synthesized magnetic Fe_3O_4@SiO2 grafting schiff's base type sorbing materials, heavy metal ion Cu2+、Zn2+And Ni2+'s
Adsorption capacity reaches 97.2mg/g, 87mg/g and 81.6mg/g respectively.Souda etc. passes through 2- amino 2- methyl 1- propane sulfonic acid and magnetic
The reaction of Fe3O4 nano-particles prepares magnetic hydrogel, heavy metal ion Zn2+And Cd2+Adsorption capacity be above it is common non-
Magnetic hydrogel.Feng etc. is prepared for magnetic hydroxylapatite adsorbent, heavy metal ion Cd2+And Zn2+Theoretical maximum inhale
Attached capacity is respectively 1.964mmol/g and 2.151mmol/g.Zheng Genwu uses emulsion-crosslinking method by chitosan and Fe3O4 nanometers
Matrix is compound to obtain chitosan/Fe3O4 magnetic microspheres, aqueous solution Cu2+Adsorption capacity reach 78.15mg/g.Zhu etc. prepares magnetic
Fe3O4/ cellulose simultaneously uses it for aqueous solution heavy metal ion Mn2+、Pb2+And Cr3+Absorption, find magnetic Fe3O4/ cellulose
Heavy metal ion adsorbed performance and recycling better performances.Cheng Changjing etc. is using monoxone to chitosan with high deacetylation degree
Carboxy methylation processing is carried out, it then is carried out into surface graft copolymerization with magnetic Fe_3O_4 nano-particle obtains the magnetic of core shell structure
Property chitosan absorbent, heavy metal ion Cu2+Adsorption capacity be 71.43mg/g.
Although magnetic polymer adsorbent for heavy metal increasingly gets more and more people's extensive concerning and is increasingly becoming the country
Outer study hotspot, but the compatibility of magnetic nano-particle and polymeric matrix how is effectively improved, avoid magnetic nano-particle
Reunion and suppress the macroscopic view phase separation of magnetic nano-particle and polymeric matrix, be still to influence magnetic polymer adsorbent
The crucial science and Pinch technology problem of magnetic property and heavy metal ion adsorbed performance.
3rd, the content of the invention
In view of this, the purpose of the present invention is exactly to provide a kind of preparation side of magnetic polymer adsorbent for heavy metal
Method.Magnetic nano-particle is prepared using improvement chemical coprecipitation first, then respectively with γ-r-chloropropyl trimethoxyl silane and
Polyethyleneimine carries out surface modification to it, obtains polyethyleneimine-modified magnetic nano-particle, finally changes polyethyleneimine
Property magnetic nano-particle and functional monomer be copolymerized, prepare and adsorbed with multi-layer cross-linked structure and contents of many kinds of heavy metal ion
The magnetic polymer adsorbent for heavy metal of group, by polyethyleneimine-modified magnetic nano-particle, improve magnetic Nano
The compatibility of particle and polymeric matrix, pass through the polyethyleneimine macromolecular chain and polymer of magnetic nano-particle surface grafting
The physical entanglement of matrix and hydrogen bond action, the reunion of magnetic nano-particle is avoided, suppress magnetic nano-particle and polymeric matrix
Macroscopic view phase separation, realize that the heavy metal ion adsorbed magnetic of magnetic polymer intelligently separates, preferably solve common adsorbents and consolidate
Liquid separation is difficult, is also easy to produce the shortcomings that secondary pollution.
According to object of the invention it is proposed that a kind of preparation method of magnetic polymer adsorbent for heavy metal, it is special
Sign has following processing step：
A) FeCl36H2O, FeCl24H2O and deionized water are added in three-necked flask, stirred, nitrogen is protected
50~80 DEG C are warming up to after shield 30min, the ammonia spirit that mass concentration is 25~30% is then added dropwise, ammonia spirit is added dropwise
Nitrogen protection 3~6h of isothermal reaction afterwards, room temperature is cooled to, deionized water is washed 3~5 times, magnet separation, obtains magnetic nano particle
Son；The ammonia spirit and the mass ratio of deionized water that FeCl36H2O, FeCl24H2O, mass concentration are 25~30% are 10
~30:5~10：25~60:100~200；
B) magnetic nano-particle, γ-r-chloropropyl trimethoxyl silane and deionized water are added in three-necked flask and stirred
Uniformly, 50~80 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that mass concentration is 25~30%, nitrogen is then added dropwise
Room temperature is cooled to after 3~6h of protection isothermal reaction, deionized water is washed 3~5 times, magnet separation, obtains chloropropyl modified Nano
Magnetic particle；Magnetic nano-particle, γ-r-chloropropyl trimethoxyl silane, mass concentration be 25~30% ammonia spirit and go
The mass ratio of ionized water is 1~5:2~15：2~15:100~200；
C) chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water are added in three-necked flask and stirred
It is even, 40~70 DEG C are warming up to, is cooled to room temperature after 2~5h of nitrogen protection isothermal reaction, deionized water is washed 3~5 times, magnet point
From obtaining polyethyleneimine-modified magnetic nanoparticle；Chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water
Mass ratio be 1~5:1~5:100~200；
D) NaOH is dissolved in 200mL deionized waters, acrylic acid is slowly dropped to the NaOH aqueous solution in ice bath, stirring is anti-
0.5~2h is answered, part is obtained and neutralizes acrylic acid aqueous solution；By polyethyleneimine-modified magnetic nano-particle, acrylamide and friendship
Connection agent is added to part and neutralizes acrylic acid aqueous solution, stirs, and is warming up to 50~60 DEG C, adds redox initiator, draws
Send out polymerisation 3~5 hours, finally wash product 3~5 times with absolute ethyl alcohol, Magnetic Isolation, 80 DEG C of drying, crush, obtain
Magnetic polymer adsorbent for heavy metal；Acrylic acid and NaOH mol ratio are 1：0.5~0.8；Acrylic acid and acrylamide
Mass ratio be 1~5：1~5；Crosslinking agent accounts for the 0.1~0.8% of acrylic acid and acrylamide monomer quality total amount；Redox
Initiator accounts for the 0.1%~2.0% of acrylic acid and acrylamide monomer quality total amount；Polyethyleneimine-modified magnetic nano-particle
Account for the 5~30% of acrylic acid and acrylamide monomer quality total amount；
E) magnetic polymer adsorbent for heavy metal saturation magnetization is 10~30emu/g, and remanent magnetism and coercivity are equal
Go to zero, there is paramagnetism and magnetic responsiveness, be 100~1000mg/L heavy metal ion aqueous solution for initial concentration, a huge sum of money
Category ionic adsorption capacity reaches 35~450mg/g, and 50~100min reaches adsorption equilibrium, the huge sum of money after recycling utilization 5 times
Belong to ionic adsorption capacity exceedes first time adsorption capacity 85%.
Crosslinking agent used in the present invention is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, a contracting second
Diol acrylate, tirethylene glycol double methacrylate, 1,3- propane diols double methacrylate, trimethylolpropane tris acrylic acid
Ester, pentaerythritol triacrylate, GMA and polyethyleneglycol diacrylate.
Redox initiator used in the present invention includes Oxidizing and Reducing Agents, and oxidant is selected from ammonium persulfate, mistake
Potassium sulfate and sodium peroxydisulfate, reducing agent are selected from sodium hydrogensulfite, sodium sulfite, sodium thiosulfate and ferrous sulfate.
Heavy metal ion used in the present invention is selected from Cd2+、Cu2+、Pb2+、Ni2+、Cr3+And Cr6+。
Advantages of the present invention and effect are：
1) polymerisation is directly carried out in aqueous, and non-environmental-pollution, method is simple, is protected without nitrogen, because
This eliminates nitrogen device, reduces the Meteorological of equipment.
2) by polyethyleneimine-modified magnetic nano-particle, the compatible of magnetic nano-particle and polymeric matrix is improved
Property, made by the polyethyleneimine macromolecular chain of magnetic nano-particle surface grafting and the physical entanglement of polymeric matrix and hydrogen bond
With avoiding the reunion of magnetic nano-particle, suppress the macroscopic view phase separation of magnetic nano-particle and polymeric matrix, realize that magnetic is gathered
The heavy metal ion adsorbed magnetic of compound intelligently separates, and preferably solves common adsorbents separation of solid and liquid hardly possible, is also easy to produce secondary pollution
The shortcomings that.
3) polyethyleneimine-modified magnetic nano-particle and functional monomer are copolymerized, preparing has multi-layer crosslinking
The magnetic polymer adsorbent for heavy metal of structure and contents of many kinds of heavy metal ion adsorption group, passes through the association of a variety of adsorption groups
Same effect, further improve the absorption property of magnetic polymer adsorbent heavy metal ion；
The hysteresis property of magnetic polymer adsorbent for heavy metal of the present invention, heavy metal ion adsorbed speed,
Adsorption capacity, recycling utilization performance measurement method are as follows.
Using the hysteresis of LDJ-9600 types vibration magnetometer (VSM) measure magnetic polymer adsorbent for heavy metal
Energy.
By the magnetic polymer weight that the heavy metal ion aqueous solution and 0.2g that concentration is 100~1000mg/L are dry, finely ground
Metal ion adsorbent is put into 250mL conical flasks, is subsequently placed in oscillator and is vibrated absorption, is sampled after vibrating certain time,
Using the absorbance of atomic absorption spectrometry sample, each sample is measured 3 times and averaged, heavy metal ion adsorbed amount qt
With adsorption capacity qeIt is calculated as follows respectively：
qt(mg/g)={ (C0-Ct)V}/m (1)
qe(mg/g)={ (C0-Ce)V}/m (2)
Wherein C0、CtAnd CeRespectively heavy metal ion initial concentration, vibration absorption certain time concentration of heavy metal ion,
Heavy metal ion adsorbed equilibrium concentration (mg.L-1), V are liquor capacity (L), and m is magnetic polymer adsorbent for heavy metal
Quality (g).
The magnetic polymer adsorbent of saturation absorption heavy metal ion is shaken into solution with 50mL 0.5mol/L hydrochloric acid solution
Inhale, use atomic absorption spectrometry heavy metal ions concentration in solution after desorbing certain time, put down until reaching desorption
Weighing apparatus.Magnetic polymer adsorbent after desorption is dried and crushed, then heavy metal ion is inhaled again under the same conditions
It is attached, using the heavy metal ion adsorbed capacity of atomic absorption spectrometry magnetic polymer adsorbent, and with first time with much money
The adsorption capacity of category ion compares, and characterizes the recycling utilization performance of magnetic polymer adsorbent for heavy metal, repeatedly
Regeneration cycle adsorbs 5 times to assess the recycling utilization performance of magnetic polymer adsorbent for heavy metal.
4th, embodiment
For a better understanding of the present invention, present disclosure is expanded on further with reference to embodiment, but it is of the invention
Content be not limited solely to the following examples.
Embodiment 1：
19.6g FeCl36H2O and 7.2g FeCl24H2O and 150mL deionized waters are added in three-necked flask,
Stir, be warming up to 60 DEG C after nitrogen protection 30min, the ammonia spirit that 50g mass concentrations are 25~30%, ammonia is then added dropwise
Rear nitrogen protection isothermal reaction 5h is added dropwise in the aqueous solution, is cooled to room temperature, and deionized water is washed 3 times, magnet separation, obtains magnetic
Property nano-particle；1g magnetic nano-particles, 2g γ-r-chloropropyl trimethoxyl silane and 100mL deionized waters are added to three mouthfuls
Stirred in flask, be warming up to 60 DEG C after nitrogen protection 30min, it is molten that the ammoniacal liquor that 2g mass concentrations are 25~30% is then added dropwise
Liquid, nitrogen are cooled to room temperature after protecting isothermal reaction 5h, and deionized water is washed 5 times, magnet separation, obtains chloropropyl modified Nano
Magnetic particle.1g chloropropyl modified Nanos magnetic particle, 1g polyethyleneimines and 100mL deionized waters are added to three-necked flask
In stir, be warming up to 40 DEG C, be cooled to room temperature after nitrogen protection isothermal reaction 5h, deionized water is washed 3 times, magnet point
From obtaining polyethyleneimine-modified magnetic nanoparticle.
9g NaOH are dissolved in 200mL deionized waters, 24g acrylic acid is slowly dropped to the NaOH aqueous solution in ice bath,
Stirring reaction 2h, obtain part and neutralize acrylic acid aqueous solution；By 12g polyethyleneimine-modifieds magnetic nanoparticle, 16g acryloyls
Amine and 0.12g ethylene glycol diacrylates are added to part and neutralize acrylic acid aqueous solution, stir, and are warming up to 60 DEG C, add
0.48g ammonium persulfates and 0.16g sodium hydrogensulfites, initiated polymerization 3 hours, finally product is washed 3 times with absolute ethyl alcohol,
Magnetic Isolation, 80 DEG C of drying, crushes, obtains magnetic polymer adsorbent for heavy metal, saturation magnetization 15.5emu/
G, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；For the Cd that initial concentration is 100mg/L2+、Ni2+、
Pb2+And Cu2+The aqueous solution, magnetic polymer adsorbent for heavy metal Cd2+、Ni2+、Pb2+And Cu2+Adsorption capacity respectively reaches
41mg/g, 35mg/g, 54mg/g and 45mg/g, 100min reach adsorption equilibrium, the heavy metal ion after recycling utilization 5 times
Cd2+、Ni2+、Pb2+And Cu2+Adsorption capacity exceedes the 85% of first time adsorption capacity.
Embodiment 2：
30gFeCl36H2O and 10gFeCl24H2O and 200mL deionized waters are added in three-necked flask, stirred
Uniformly, 70 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that 60g mass concentrations are 25~30% is then added dropwise, ammoniacal liquor is molten
Rear nitrogen protection isothermal reaction 4h is added dropwise in liquid, is cooled to room temperature, and deionized water is washed 5 times, magnet separation, is obtained magnetic and is received
Rice corpuscles；5g magnetic nano-particles, 15g γ-r-chloropropyl trimethoxyl silane and 200mL deionized waters are added to three-necked flask
In stir, be warming up to 70 DEG C after nitrogen protection 30min, the ammonia spirit that 15g mass concentrations are 25~30% be then added dropwise,
Room temperature is cooled to after nitrogen protection isothermal reaction 4h, deionization is washed 5 times or so, magnet separation, obtains chloropropyl modified Nano
Magnetic particle.2.5g chloropropyl modified Nanos magnetic particle, 3g polyethyleneimines and 150mL deionized waters are added to three mouthfuls of burnings
Stirred in bottle, be warming up to 70 DEG C, be cooled to room temperature after nitrogen protection isothermal reaction 2h, deionized water is washed 5 times, magnet point
From obtaining polyethyleneimine-modified magnetic nanoparticle.
7.2g NaOH are dissolved in 200mL deionized waters, it is water-soluble that 20g acrylic acid is slowly dropped into NaOH in ice bath
Liquid, stirring reaction 0.5h, obtain part and neutralize acrylic acid aqueous solution；By 6g polyethyleneimine-modifieds magnetic nanoparticle, 20g third
Acrylamide and 0.08g diethylene glycol double methacrylates are added to part and neutralize acrylic acid aqueous solution, stir, are warming up to 60
DEG C, add 0.36g sodium peroxydisulfates and 0.12g sodium hydrogensulfites, initiated polymerization 3 hours, finally by product absolute ethyl alcohol
Washing 5 times, Magnetic Isolation, 80 DEG C of drying, crush, obtain magnetic polymer adsorbent for heavy metal, saturation magnetization is
8.6emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；For the Cu that initial concentration is 300mg/L2 +、Ni2+、Cr3+And Cr6+The aqueous solution, magnetic polymer adsorbent for heavy metal Cu2+、Ni2+、Cr3+And Cr6+Adsorption capacity is distinguished
Reach 105mg/g, 83mg/g, 76mg/g and 62mg/g, 85min reaches adsorption equilibrium, the heavy metal after recycling utilization 5 times
Ion Cu2+、Ni2+、Cr3+And Cr6+Adsorption capacity exceedes the 85% of first time adsorption capacity.
Embodiment 3：
10gFeCl36H2O and 5gFeCl24H2O and 100mL deionized waters are added in three-necked flask, stirring is equal
It is even, 80 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that 25g mass concentrations are 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 3h is added dropwise, is cooled to room temperature, deionized water is washed 4 times, magnet separation, obtains magnetic Nano
Particle；3g magnetic nano-particles, 8g γ-r-chloropropyl trimethoxyl silane and 150mL deionized waters are added in three-necked flask
Stir, be warming up to 80 DEG C after nitrogen protection 30min, the ammonia spirit that 10g mass concentrations are 25~30%, nitrogen is then added dropwise
Room temperature is cooled to after gas shielded isothermal reaction 3h, deionized water is washed 3 times, magnet separation, obtains chloropropyl modified Nano magnetic
Particle.5g chloropropyl modified Nanos magnetic particle, 5g polyethyleneimines and 200mL deionized waters are added in three-necked flask and stirred
Mix uniformly, be warming up to 60 DEG C, room temperature is cooled to after nitrogen protection isothermal reaction 3h, deionized water is washed 5 times, magnet separation, is obtained
To polyethyleneimine-modified magnetic nanoparticle.
5.4g NaOH are dissolved in 200mL deionized waters, it is water-soluble that 16g acrylic acid is slowly dropped into NaOH in ice bath
Liquid, stirring reaction 1h, obtain part and neutralize acrylic acid aqueous solution；By 8g polyethyleneimine-modifieds magnetic nanoparticle, 24g propylene
Acid amides and 0.10g tirethylene glycol double methacrylates are added to part and neutralize acrylic acid aqueous solution, stir, are warming up to 50
DEG C, add 0.54g potassium peroxydisulfates and 0.18g sodium thiosulfate, initiated polymerization 5 hours, finally by product absolute ethyl alcohol
Washing 3 times, Magnetic Isolation, 80 DEG C of drying, crush, obtain magnetic polymer adsorbent for heavy metal, saturation magnetization is
11.2emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；It is 600mg/L's for initial concentration
Pb2+、Cu2+、Cd2+And Ni2+The aqueous solution, magnetic polymer adsorbent for heavy metal Pb2+、Cu2+、Cd2+And Ni2+Adsorption capacity
Respectively reach 214mg/g, 166mg/g, 148mg/g and 115mg/g, 70min reaches adsorption equilibrium, after recycling utilization 5 times
Heavy metal ion Pb2+、Cu2+、Cd2+And Ni2+Adsorption capacity exceedes the 85% of first time adsorption capacity.
Embodiment 4：
15gFeCl36H2O and 6gFeCl24H2O and 150mL deionized waters are added in three-necked flask, stirring is equal
It is even, 50 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that 35g mass concentrations are 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 6h is added dropwise, is cooled to room temperature, deionized water is washed 5 times, magnet separation, obtains magnetic Nano
Particle；2.5g magnetic nano-particles, 5g γ-r-chloropropyl trimethoxyl silane and 100mL deionized waters are added to three-necked flask
In stir, be warming up to 50 DEG C after nitrogen protection 30min, the ammonia spirit that 6g mass concentrations are 25~30% be then added dropwise,
Room temperature is cooled to after nitrogen protection isothermal reaction 6h, deionized water is washed 5 times, magnet separation, obtains chloropropyl modified Nano magnetic
Property particle.Chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water are added in three-necked flask and stirred,
50 DEG C are warming up to, room temperature is cooled to after nitrogen protection isothermal reaction 4h, deionized water is washed 3 times, magnet separation, obtains polyethylene
Imine modified magnetic nanoparticle.
9g NaOH are dissolved in 200mL deionized waters, 24g acrylic acid is slowly dropped to the NaOH aqueous solution in ice bath,
Stirring reaction 2h, obtain part and neutralize acrylic acid aqueous solution；By 2g polyethyleneimine-modifieds magnetic nanoparticle, 16g acryloyls
Amine and 0.16g 1,3-PD double methacrylates are added to part and neutralize acrylic acid aqueous solution, stir, are warming up to 50 DEG C,
0.60g potassium peroxydisulfates and 0.20g sodium sulfites are added, initiated polymerization 5 hours, product is finally washed 5 with absolute ethyl alcohol
It is secondary, Magnetic Isolation, 80 DEG C of drying, crush, obtain magnetic polymer adsorbent for heavy metal, saturation magnetization is
3.5emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；For the Pb that initial concentration is 800mg/L2 +、Cu2+、Cd2+And Cr3+The aqueous solution, magnetic polymer adsorbent for heavy metal Pb2+、Cu2+、Cd2+And Cr3+Adsorption capacity is distinguished
Reach 324mg/g, 186mg/g, 153mg/g and 98mg/g, 60min reaches adsorption equilibrium, the huge sum of money after recycling utilization 5 times
Belong to ion Pb2+、Cu2+、Cd2+And Cr3+Adsorption capacity exceedes the 85% of first time adsorption capacity.
Embodiment 5：
20gFeCl36H2O and 8gFeCl24H2O and 200mL deionized waters are added in three-necked flask, stirring is equal
It is even, 70 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that 50g mass concentrations are 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 4h is added dropwise, is cooled to room temperature, deionized water is washed 4 times, magnet separation, obtains magnetic Nano
Particle；4g magnetic nano-particles, 12g γ-r-chloropropyl trimethoxyl silane and 200mL deionized waters are added in three-necked flask
Stir, be warming up to 80 DEG C after nitrogen protection 30min, the ammonia spirit that 12g mass concentrations are 25~30%, nitrogen is then added dropwise
Room temperature is cooled to after gas shielded isothermal reaction 3h, deionized water is washed 3 times, magnet separation, obtains chloropropyl modified Nano magnetic
Particle.3g chloropropyl modified Nanos magnetic particle, 2g polyethyleneimines and 150mL deionized waters are added in three-necked flask and stirred
Mix uniformly, be warming up to 40 DEG C, room temperature is cooled to after nitrogen protection isothermal reaction 5h, deionized water is washed 5 times, magnet separation, is obtained
To polyethyleneimine-modified magnetic nanoparticle.
8g NaOH are dissolved in 200mL deionized waters, 24g acrylic acid is slowly dropped to the NaOH aqueous solution in ice bath,
Stirring reaction 2h, obtain part and neutralize acrylic acid aqueous solution；By 4g polyethyleneimine-modifieds magnetic nanoparticle, 18g acryloyls
Amine and 0.10g N, N '-methylene-bisacrylamide are added to part and neutralize acrylic acid aqueous solution, stir, are warming up to 50
DEG C, add 0.62g ammonium persulfates and 0.21g sodium hydrogensulfites, initiated polymerization 5 hours, finally by product absolute ethyl alcohol
Washing 3 times, Magnetic Isolation, 80 DEG C of drying, crush, obtain magnetic polymer adsorbent for heavy metal, saturation magnetization is
5.9emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism and magnetic responsiveness；It is 1000mg/L's for initial concentration
Pb2+、Cu2+、Cd2+And Ni2+The aqueous solution, magnetic polymer adsorbent for heavy metal Pb2+、Cu2+、Cd2+And Ni2+Adsorption capacity
Respectively reach 450mg/g, 236mg/g, 190mg/g and 132mg/g, 50min reaches adsorption equilibrium, after recycling utilization 5 times
Heavy metal ion Pb2+、Cu2+、Cd2+And Ni2+Adsorption capacity exceedes the 85% of first time adsorption capacity.
Claims (4)
1. a kind of preparation method of magnetic polymer adsorbent for heavy metal, it is characterised in that have following processing step：
FeCl36H2O, FeCl24H2O and deionized water are added in three-necked flask, stirred, nitrogen protection
50~80 °C are warming up to after 30min, the ammonia spirit that mass concentration is 25~30% is then added dropwise, after ammonia spirit is added dropwise
Nitrogen protects 3~6h of isothermal reaction, is cooled to room temperature, and deionized water is washed 3~5 times, magnet separation, obtains magnetic nano particle
Son；The ammonia spirit and the mass ratio of deionized water that FeCl36H2O, FeCl24H2O, mass concentration are 25~30% are 10
~30:5~10：25~60:100~200；
Magnetic nano-particle, γ-r-chloropropyl trimethoxyl silane and deionized water are added in three-necked flask and stirred, nitrogen
50~80 °C are warming up to after gas shielded 30min, the ammonia spirit that mass concentration is 25~30%, nitrogen protection constant temperature is then added dropwise
Room temperature is cooled to after 3~6h of reaction, deionized water is washed 3~5 times, magnet separation, obtains chloropropyl modified Nano magnetic particle；
Magnetic nano-particle, γ-r-chloropropyl trimethoxyl silane, mass concentration are 25~30% ammonia spirit and the matter of deionized water
Amount is than being 1~5:2~15：2~15:100~200；
Chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water are added in three-necked flask and stirred, is risen
For temperature to 40~70 °C, nitrogen is cooled to room temperature after protecting 2~5h of isothermal reaction, and deionized water is washed 3~5 times, magnet separation, obtains
To polyethyleneimine-modified magnetic nanoparticle；The matter of chloropropyl modified Nano magnetic particle, polyethyleneimine and deionized water
Amount is than being 1~5:1~5:100~200；
NaOH is dissolved in 200mL deionized waters, acrylic acid is slowly dropped to the NaOH aqueous solution, stirring reaction 0.5 in ice bath
~2h, obtain part and neutralize acrylic acid aqueous solution；Polyethyleneimine-modified magnetic nano-particle, acrylamide and crosslinking agent are added
Enter to part and neutralize acrylic acid aqueous solution, stir, be warming up to 50~60 DEG C, add redox initiator, trigger polymerization
Reaction 3~5 hours, finally washs product 3~5 times with absolute ethyl alcohol, Magnetic Isolation, 80 DEG C of drying, crushes, obtains magnetic and gather
Compound adsorbent for heavy metal；Acrylic acid and NaOH mol ratio are 1：0.5~0.8；The quality of acrylic acid and acrylamide
Than for 1~5：1~5；Crosslinking agent accounts for the 0.1~0.8% of acrylic acid and acrylamide monomer quality total amount；Redox initiator
Account for the 0.1%~2.0% of acrylic acid and acrylamide monomer quality total amount；The mol ratio of Oxidizing and Reducing Agents is 1~2：1；It is poly-
Aziridine modified magnetic nano-particle accounts for the 5~30% of acrylic acid and acrylamide monomer quality total amount；
Magnetic polymer adsorbent for heavy metal saturation magnetization is 3.5~15.5 emu/g, and remanent magnetism and coercivity become
In zero, there is paramagnetism and magnetic responsiveness, be 100~1000mg/L heavy metal ion aqueous solution for initial concentration, heavy metal
Ionic adsorption capacity reaches 35~450mg/g, and 50~100min reaches adsorption equilibrium, the heavy metal after recycling utilization 5 times
Ionic adsorption capacity exceedes the 85% of first time adsorption capacity.
A kind of 2. preparation method of magnetic polymer adsorbent for heavy metal according to claim 1, it is characterised in that：
Described crosslinking agent is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, diethylene glycol double methacrylate,
Tirethylene glycol double methacrylate, 1,3- propane diols double methacrylate, trimethylolpropane trimethacrylate, pentaerythrite 3 third
Olefin(e) acid ester, GMA and polyethyleneglycol diacrylate.
A kind of 3. preparation method of magnetic polymer adsorbent for heavy metal according to claim 1, it is characterised in that：
Described redox initiator includes Oxidizing and Reducing Agents, and oxidant is selected from ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate,
Reducing agent is selected from sodium hydrogensulfite, sodium sulfite, sodium thiosulfate and ferrous sulfate.
A kind of 4. preparation method of magnetic polymer adsorbent for heavy metal according to claim 1, it is characterised in that：
Described heavy metal ion is selected from Cd2+、Cu2+、Pb2+、Ni2+、Cr3+And Cr6+。
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