CN109569544A - A kind of preparation method of amino and carboxyl-functional magnetic microsphere compound adsorbent - Google Patents
A kind of preparation method of amino and carboxyl-functional magnetic microsphere compound adsorbent Download PDFInfo
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- CN109569544A CN109569544A CN201910103174.3A CN201910103174A CN109569544A CN 109569544 A CN109569544 A CN 109569544A CN 201910103174 A CN201910103174 A CN 201910103174A CN 109569544 A CN109569544 A CN 109569544A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000004005 microsphere Substances 0.000 title claims abstract description 36
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 33
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000002131 composite material Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- -1 aminopropyl Chemical group 0.000 claims description 31
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005576 amination reaction Methods 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- 235000019394 potassium persulphate Nutrition 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229920006037 cross link polymer Polymers 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000003446 ligand Substances 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 3
- 125000003368 amide group Chemical group 0.000 abstract description 2
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000002077 nanosphere Substances 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- 238000010521 absorption reaction Methods 0.000 description 25
- 239000010949 copper Substances 0.000 description 9
- 239000003651 drinking water Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229960003511 macrogol Drugs 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
-
- 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
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- 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)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses the preparation methods of a kind of amino and carboxyl-functional magnetic microsphere compound adsorbent, are successfully prepared Fe using solvent thermal process first3O4Nanoparticle, with Fe3O4Magnetic nano-particle is as magnetic core, then in Fe3O4Electronegative graphene oxide is assembled in the positively charged Fe of amido modified mistake by amino in surface modification by electrostatic interaction3O4Outside nanosphere, finally by suspension polymerization to Fe3O4/ GO microsphere surface is modified the Fe for preparing amino and carboxyl difunctionalization3O4/GO‑NH2/ COOH magnetic composite microsphere；Succeed the big specific surface area of graphene oxide, strong characterization of adsorption and magnetic Fe3O4The characteristic that efficiently separates of nanometer particle material combines, simultaneously because a large amount of amino of microsphere surface, carboxyl have stronger chelating ligands ability to metal ion, greatly improve adsorbent selectivity, magnetic composite microsphere of the invention have many advantages, such as large amount of adsorption, easily separated, removal rate is high and easy to operate, Yi Huishou, pollution it is small, have good practical application value.
Description
Technical field
The present invention relates to a kind of preparation methods of adsorbent, and in particular to a kind of amino and carboxyl-functional magnetic microsphere are multiple
Close the preparation method of adsorbent.
Background technique
The mankind have the history of more than one thousand years using heavy metal, and in use, heavy metal ion inevitably passes through
Number of ways enters water body, due to its persistence in water body and is difficult to removal, and heavy metal ion is caused to be easy to plant dynamic
It is enriched in object and human body, so as to cause the extensive attention of researcher；It, at present can there are many method by years of researches
The heavy metal ion in water removal, such as chemical heavy, electrochemistry, membrane filtration, ion exchange and absorption method are gone, in these methods
In, absorption method is since it has many advantages, such as at low cost, easy to operate and by researcher favor, and the key of absorption method is
Find suitable sorbent material；In addition to the adsorbents such as traditional active carbon, zeolite, Recent study personnel use shell in succession
The new adsorbents such as glycan, lignin, zeroth order Nanoscale Iron achieve a series of progress in adsorbing domain.
Compare other adsorbents, and graphene oxide (GO) has higher specific surface area, and it also has and largely contains
The features such as oxygen functional group and good water dispersible, this make GO as adsorbent go water removal in heavy metal ion potentiality phase
Physical and chemical condition higher than other adsorbents but special also limits it as a kind of adsorbent material in water treatment field
It uses, if GO has good hydrophily, degree of scatter is higher in water, so being difficult after absorption by it from solution
It separates；Selectivity is lacked to the absorption of heavy metal ion in water；Since pi-pi bond is easy to be mutually interpolymerized with the influence of Van der Waals force
Collection；Also there is genotoxic potential etc. to organism in water.
It is to improve absorption property and open using the modification of the func-tional ligands such as polyacrylic acid, amino/sulfhydryl silane, acrylamide
The effective ways of new adsorbent are sent out, functionalization often can be with functional group and integrate the strong NH of coordination ability to metal2、COOH、
SH etc.；Conventional adsorbent is also faced with that difficult recycling, reusing be poor, problem of process complexity in adsorption operations simultaneously, nanometer
Fe3O4It is a kind of widely used superparamagnetic iron oxides in the preparation of magnetic function composite material, by Fe3O4With traditional material
It can effectively solve the above problems in conjunction with building adsorbent.
Summary of the invention
That in response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of adsorbances is high, selectivity is strong and is easy to
The preparation method of a kind of amino and carboxyl-functional magnetic microsphere compound adsorbent of quick separating.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of amino and carboxyl-functional magnetic microsphere compound adsorbent, includes the following steps:
S1, nanometer Fe3O4Preparation: under stirring condition, using ethylene glycol as solvent, 1:5:1.5 in mass ratio is sequentially added
FeCl3·6H2O, sodium acetate, Macrogol 4000 prepare nanometer Fe using hydro-thermal method after mixing3O4；
S2, amination nanometer Fe3O4Preparation: take nanometer Fe made from step S13O4It is dissolved in ethylene glycol, aminopropyl three is added
Methoxy silane flows back for 24 hours at 60-75 DEG C；Acquired solution is first washed, ethyl alcohol is washed again, be then dried to obtain amination nanometer
Fe3O4；The nanometer Fe3O4Solid-to-liquid ratio with aminopropyl trimethoxysilane is (0.5-1) g:1mL；
S3、Fe3O4The preparation of/GO composite material: by amination nanometer Fe3O4It is dissolved in ethylene glycol, being configured to mass concentration is
The solution A of 1.0mg/mL；Graphene oxide is dissolved in NaOH aqueous solution, and ultrasonic disperse 30min, being configured to mass concentration is
The B solution of 0.5mg/mL；By solution A and B solution, 1:1.5-2 is mixed by volume under mechanical stirring, continues to stir 2-3h；Institute
It obtains solution to be first washed with distilled water with ethanol washing, again, dry obtained Fe3O4/ GO composite material；
S4、Fe3O4/GO-NH2The preparation of/COOH compound adsorbent: Fe made from 0.1-0.5g step S3 is weighed3O4/ GO is compound
Material is scattered in organic solvent, under stirring condition, methacrylic acid and acrylamide monomer is added, adds N, N- methylene
Bisacrylamide crosslinker, potassium peroxydisulfate initiator, 60-80 DEG C of stirring in water bath 4-6h, after reaction, product magnet point
From, and wash, drying to obtain Fe3O4/GO-NH2/ COOH compound adsorbent；The Fe3O4/ GO composite material and the methyl
The mass ratio of acrylic monomers is 1:10, the methacrylic acid, acrylamide monomer, N, the crosslinking of N- methylene-bisacrylamide
Agent, potassium peroxydisulfate molar ratio be 1:0.8-1.5:2-5:2-3.
Preferably, methacrylic acid described in step S4, acrylamide monomer, N, the crosslinking of N- methylene-bisacrylamide
Agent, potassium peroxydisulfate molar ratio be 1:1.2:4:2.5.
Preferably, organic solvent described in step S4 is mixed by dehydrated alcohol and water according to volume ratio for 2:1.
Preferably, drying condition is dry 12h at 40 DEG C in step S4.
Preferably, hydrothermal reaction condition is 200 DEG C of reaction 10h in step S1.
Preferably, nanometer Fe described in step S23O4Solid-to-liquid ratio with aminopropyl trimethoxysilane is 1g:1mL.
Preferably, 1:1.8 is mixed by volume for solution A and B solution in step S3.
The present invention also provides the preparation method systems of a kind of amino and carboxyl-functional magnetic microsphere compound adsorbent
The compound adsorbent obtained is for the heavy metal ion in adsorbed water body.
Preferably, multiple made from the preparation method of a kind of described amino and carboxyl-functional magnetic microsphere compound adsorbent
Adsorbent is closed for the metal copper ion in adsorbed water body.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention prepares Fe using solvent-thermal process3O4Nanoparticle, with Fe3O4Magnetic nano-particle is used as magnetic core,
Then in Fe3O4Electronegative graphene oxide is assembled in the band of amido modified mistake by amino in surface modification by electrostatic interaction
The Fe of positive electricity3O4Outside nanosphere, the Fe of this magnetism3O4/ GO microballoon can be by the big specific surface area of graphene oxide, strong suction
Attached characteristic combines with the characteristic that efficiently separates of magnetic material, prepares the big, removal rate to adsorption of metal ions amount in water body
Height, the magnetic composite adsorbent microballoon with good practical application potentiality.
(2) using methacrylic acid and acrylamide as monomer, N, N- methylene-bisacrylamide is crosslinking agent, potassium peroxydisulfate
For initiator, by suspension polymerization to Fe3O4/ GO microsphere surface is modified the magnetic for preparing amino and carboxyl difunctionalization
Property complex microsphere, a large amount of amino of microsphere surface, carboxyl have stronger chelating ligands ability to metal ion, can mention significantly
Rise the absorption property and selectivity of adsorbent.
(3) amino and carboxyl-functional magnetic microsphere compound adsorbent that the present invention is prepared are applied in wastewater treatment
Have many advantages, such as that easy to operate, at low cost, Yi Huishou, pollution are small.
Detailed description of the invention
Fig. 1 is Fe made from embodiment 13O4/GO-NH2The scanning electron microscope phenogram of/COOH compound adsorbent.
Fig. 2 is different pH value to Fe made from embodiment 13O4/GO-NH2/ COOH compound adsorbent is to Cu2+The shadow of adsorbance
Ring result figure.
Fig. 3 is adsorption time to Fe made from embodiment 13O4/GO-NH2/ COOH compound adsorbent is to Cu2+The shadow of adsorbance
Ring result figure.
Fig. 4 is temperature to Fe made from embodiment 13O4/GO-NH2/ COOH compound adsorbent is to Cu2+The influence of adsorbance
Result figure.
Fig. 5 is Fe made from embodiment 13O4/GO-NH2/ COOH compound adsorbent is to Cu in drinking water2+Absorption result figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated；It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention；Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
The Fe that the present invention is prepared3O4/GO-NH2/ COOH compound adsorbent is to the heavy metal ion in water, such as Cu2+、
Cd2+、Pb2+、Cr6+All have preferable absorption property, the Fe in following specific embodiments to obtain3O4/GO-NH2/ COOH is multiple
Adsorbent is closed to Cu in water2+Absorption for illustrate.
Embodiment 1
A kind of preparation method of amino and carboxyl-functional magnetic microsphere compound adsorbent, includes the following steps:
S1, nanometer Fe3O4Preparation: by 1.0gFeCl3·6H2O is dissolved in 20mL ethylene glycol solution, after magnetic agitation 30min successively
5.0g sodium acetate, 1.5g Macrogol 4000,30 ~ 60min of magnetic agitation is added；Acquired solution is transferred to hydrothermal reaction kettle
In, 200 DEG C of reaction 10h；
S2, amination nanometer Fe3O4Preparation: by 1.0g nanometer Fe3O4It is dissolved in ultrasonic disperse 30min in 50mL ethylene glycol, is added
1.0mL aminopropyl trimethoxysilane flows back for 24 hours at 60-75 DEG C；Acquired solution is first washed, ethyl alcohol is washed again, then 60 DEG C it is true
The dry 2h of sky, obtains amination nanometer Fe3O4；
S3、Fe3O4The preparation of/GO composite material: by amination nanometer Fe3O4It is dissolved in isopropanol, being configured to mass concentration is
The solution A of 1.0g/L；Graphene oxide is dissolved in NaOH aqueous solution simultaneously ultrasonic disperse 30min, being configured to mass concentration is
The B solution of 0.5g/L；By solution A and B solution, 1:1.8 is mixed by volume under mechanical stirring, continues 2 ~ 3h of stirring；Gained is molten
Liquid is first washed with distilled water with ethanol washing, again, and Fe3O4/GO compound material is made in 40 DEG C of vacuum drying for 24 hours；
S4、Fe3O4/GO-NH2The preparation of/COOH compound adsorbent: Fe made from 0.1-0.5g step S3 is weighed3O4/ GO is compound
Material is scattered in by the in the mixed solvent of 30mL ethyl alcohol and 15mL water, and under stirring condition, methacrylic acid and acrylamide is added
Monomer adds N, N- methylene-bisacrylamide crosslinking agent, potassium peroxydisulfate initiator, 60-80 DEG C of stirring in water bath 4-6h, reaction
After, product is separated with magnet, and is washed, and dry 12h obtains Fe at 40 DEG C3O4/GO-NH2/ COOH compound adsorbent；Institute
State Fe3O4The mass ratio of/GO composite material and the methacrylic acid monomer is 1:10, the methacrylic acid, acrylamide list
Body, N, N- methylene-bisacrylamide crosslinking agent, potassium peroxydisulfate molar ratio be 1:1.2:4:2.5.
Fig. 1 is Fe made from the present embodiment3O4/GO-NH2The scanning electron microscope phenogram of/COOH compound adsorbent,
By can see clearly that Fe in figure3O4Magnetic bead surfaces have wrapped up a lamellar structure and there is the substance of fold at edge, it was demonstrated that
Graphene oxide has been assembled in Fe3O4Surface, while can be seen that Fe3O4Microsphere surface has wrapped up one layer of very smooth figure layer, says
Bright Fe3O4/ GO composite material amino and carboxyl-functional success.
Embodiment 2
A kind of preparation method of amino and carboxyl-functional magnetic microsphere compound adsorbent, includes the following steps:
S1, nanometer Fe3O4Preparation: by 1.0gFeCl3·6H2O is dissolved in 20mL ethylene glycol solution, after magnetic agitation 30min successively
5.0g sodium acetate, 1.5g Macrogol 4000,30 ~ 60min of magnetic agitation is added；Acquired solution is transferred to hydrothermal reaction kettle
In, 200 DEG C of reaction 10h；
S2, amination nanometer Fe3O4Preparation: by 0.5g nanometer Fe3O4It is dissolved in ultrasonic disperse 30min in 50mL ethylene glycol, is added
1.0mL aminopropyl trimethoxysilane flows back for 24 hours at 60-75 DEG C；Acquired solution is first washed, ethyl alcohol is washed again, then 60 DEG C it is true
The dry 2h of sky, obtains amination nanometer Fe3O4；
S3、Fe3O4The preparation of/GO composite material: by amination nanometer Fe3O4It is dissolved in isopropanol, being configured to mass concentration is
The solution A of 1.0g/L；Graphene oxide is dissolved in NaOH aqueous solution simultaneously ultrasonic disperse 30min, being configured to mass concentration is
The B solution of 0.5g/L；By solution A and B solution, 1:1.8 is mixed by volume under mechanical stirring, continues 2 ~ 3h of stirring；Gained is molten
Liquid is first washed with distilled water with ethanol washing, again, and Fe3O4/GO compound material is made in 40 DEG C of vacuum drying for 24 hours；
S4、Fe3O4/GO-NH2The preparation of/COOH compound adsorbent: Fe made from 0.1-0.5g step S3 is weighed3O4/ GO is compound
Material is scattered in by the in the mixed solvent of 30mL ethyl alcohol and 15mL water, and under stirring condition, methacrylic acid and acrylamide is added
Monomer adds N, N- methylene-bisacrylamide crosslinking agent, potassium peroxydisulfate initiator, 60-80 DEG C of stirring in water bath 4-6h, reaction
After, product is separated with magnet, and is washed, and dry 12h obtains Fe at 40 DEG C3O4/GO-NH2/ COOH compound adsorbent；Institute
State Fe3O4The mass ratio of/GO composite material and the methacrylic acid monomer is 1:10, the methacrylic acid, acrylamide list
Body, N, N- methylene-bisacrylamide crosslinking agent, potassium peroxydisulfate molar ratio be 1:1.2:4:2.5.
Embodiment 3
The present embodiment provides the preparation methods of a kind of amino and carboxyl-functional magnetic microsphere compound adsorbent, with 1 phase of embodiment
Than, the difference is that, 1:1.5 is mixed by volume for solution A and B solution in step S3.
Embodiment 4
The present embodiment provides the preparation methods of a kind of amino and carboxyl-functional magnetic microsphere compound adsorbent, with 1 phase of embodiment
Than, the difference is that, 1:2 is mixed by volume for solution A and B solution in step S3.
Embodiment 5
The present embodiment provides the preparation methods of a kind of amino and carboxyl-functional magnetic microsphere compound adsorbent, with 1 phase of embodiment
Than, the difference is that, methacrylic acid described in step S4, acrylamide monomer, N, the crosslinking of N- methylene-bisacrylamide
Agent, potassium peroxydisulfate molar ratio be 1:0.8:2:2.
Embodiment 6
The present embodiment provides the preparation methods of a kind of amino and carboxyl-functional magnetic microsphere compound adsorbent, with 1 phase of embodiment
Than, the difference is that, methacrylic acid described in step S4, acrylamide monomer, N, the crosslinking of N- methylene-bisacrylamide
Agent, potassium peroxydisulfate molar ratio be 1:1.5:5:3.
Application examples 1
Utilize Fe made from classical batch processing research embodiment 1 ~ 63O4/GO-NH2The absorption property of/COOH compound adsorbent is inhaled
Adsorbent amount is 0.56g/L in adhesion test, and all tests are repeated 3 times, wherein Cu2+Mass concentration is 100mg/L, adsorption time
For 8h, adsorption rate is measured, as a result as shown in the table.
| Group | Adsorption rate/% |
| Embodiment 1 | 99 |
| Embodiment 2 | 98 |
| Embodiment 3 | 98 |
| Embodiment 4 | 97 |
| Embodiment 5 | 96 |
| Embodiment 6 | 97 |
As upper table result it is found that Fe made from the embodiment of the present invention 1 ~ 63O4/GO-NH2/ COOH compound adsorbent all has preferably
Absorption property, and 1 adsorption effect of embodiment is best, and changes the either condition in preparation process, all can be to compound adsorbent
Absorption property have an impact, only under preparation condition defined by the present invention, above-mentioned adsorption effect could be obtained.
Application examples 2
Different pH value are inquired into Fe made from embodiment 13O4/GO-NH2/ COOH compound adsorbent is to Cu2+The influence of adsorbance,
Select Cu2+Studying pH value is 3.0 ~ 9.0, sets Cu2+Initial concentration be 100mg/L, as a result as shown in Fig. 2, as shown in Figure 2,
Increase with pH value, adsorbent is to Cu2+Adsorbance first increase and tend towards stability afterwards, quickly increase after pH > 8.0, this is because
Fe3O4/GO-NH2- the NH that/COOH compound adsorbent surface is rich in2,-COOH is to Cu2+Ion has very strong affinity, in acid
Under the conditions of property ,-NH2It is protonated in conjunction with H*, makes Cu2+There are electrostatic repulsions between magnetic microsphere surface, as pH value increases,
Electrostatic force gradually weakens, and chelating ligands effect enhancing, adsorbance is gradually increased；In addition, theoretical by isoelectric point it is found that when pH value is big
In Fe3O4/GO-NH2Microballoon is negatively charged after the isoelectric point of/COOH, and as pH value increases, the more groups of adsorbent surface go matter
Sonization, elecrtonegativity enhancing, promotes the electrostatical binding with cation, and adsorbance constantly increases, and selects pH=6.0 for Cu2+It is optimal
Adsorb pH value.
Application examples 3
Different adsorption times are inquired into Fe made from embodiment 13O4/GO-NH2/ COOH compound adsorbent is to Cu2+The shadow of adsorbance
Ring, initial pH value be optimal adsorption pH value 6, inquire into adsorption time to adsorbance influence (0,5,10,20,30,40,60,100,
140,240,300,360,480min), it draws dynamic absorption curve and obtains model of fit, as a result as shown in figure 3, by Fig. 3
It is found that adsorbent is to Cu2+Adsorbance quickly increase with the extension of adsorption time, finally tend to adsorption equilibrium.In 60min
Interior, the rate of adsorption is maximum, and adsorbance sharply increases, this stage may be mainly adsorbent surface largely accessible activation position
Point is participating in adsorbing, and as the time increases, the functional group or adsorption site of adsorbent surface gradually tend to be saturated, absorption
Adsorbance kept stable after 60min reaches final equilibrium state, Fe after 200min3O4/GO-NH2/ COOH compound adsorbent table
Face is since there are more-NH2, the groups such as-COOH and the characteristics of show absorption rapidly and efficiently.
Application examples 4
Different temperatures is inquired into Fe made from embodiment 13O4/GO-NH2/ COOH compound adsorbent is to Cu2+The influence of adsorbance,
Initial pH value is optimal adsorption pH value 6,8 h of adsorption time and different temperatures (298 K, 308 K, 318 K, 328 K) item
Under part, Fe3O4/GO-NH2/ COOH compound adsorbent is to Cu2+The influence of adsorbance sets Cu2+Initial concentration be 100mg/L,
Using Langmuir and Freundlich Adsorption Model respectively to Cu2+Adsorpting data be fitted, as a result as shown in figure 4, by
Result in figure it is found that Langmuir model to Cu2+The fitting coefficient of determination R of absorption2It is all larger than Freundlich model, is shown
Langmuir model can preferably describe Fe3O4/GO-NH2/ COOH compound adsorbent is to Cu2+Adsorption process；According to
The Cu that Langmuir model calculates2+Maximal absorptive capacity is respectively 210.98mg/g；Langmuir is on adsorbent uniform outer surface
Single layer, reversible adsorption and have limited site, the activation energy of adsorbent combination adsorption molecule is equal, thus it could be speculated that
Fe3O4/GO-NH2/ COOH compound adsorbent adsorption site is evenly distributed, to Cu2+Be adsorbed as monolayer adsorption.
Application examples 5
Investigate Fe made from embodiment 13O4/GO-NH2/ COOH compound adsorbent is to Cu in drinking water2+Adsorption process, absorption examination
Testing middle adsorbent amount is 0.56g/L, and all tests are repeated 3 times, as a result as shown in figure 5, being in first to increase to tend to balance afterwards
Trend, to Cu2+Absorption percentage be 98.94%, residue Cu in drinking water after absorption2+Concentration be 0.0021mg/L, symbol
Close Cu in drinking water as defined in the World Health Organization (WTO)2+Limit standard, therefore, Fe3O4/GO-NH2/ COOH composite adsorption
Agent can be used for removing the Cu of trace in Drinking Water2+, Adsorption of Cu is eluted with 0.1mol/LHCI solution2+Magnetic microsphere afterwards,
Three times after absorb-elute circulation, Cu2+Eluting rate be 91%, show magnetic microsphere compound adsorbent to Cu2+The repetition benefit of absorption
It is good with property.
Change in conclusion the present invention has carried out surface amino groups carboxyl to magnetic oxygenated graphene microballoon by suspension polymerization
Property, to be prepared for novel Fe3O4/GO-NH2/ COOH compound adsorbent simultaneously is used to remove the Cu in aqueous solution2+, which exists
Magnetic core crystal form is consistent in preparation process, and modified specific surface area increases, and adsorption site increases, and the absorption property of material changes
Kind, a large amount of amino of microsphere surface, carboxyl etc. have different state of ionization and nucleophilie nucleus ability, adsorbent pair in different pH values
Cu2+Absorption meet the quasi- second-level model of dynamics and Langmuir adsorption isotherm model, and to Cu2+Maximal absorptive capacity is reachable
210.98mg/g shows material to Cu2+Absorption be physical chemistry double action, be adsorbed as autonomous adsorption process and be uniformly single
Layer absorption；And adsorbent is to actually drinking Cu in some water samples2+Removal effect it is ideal so that before the adsorbent has applications well
Scape.
The above, only of the invention illustrates embodiment, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, that makes several changes
It also should be regarded as protection scope of the present invention into supplement；All those skilled in the art, do not depart from spirit of that invention and
In the case where range, using the equivalent variations of a little change, modification and differentiation that disclosed above technology contents are made, it is
Equivalent embodiment of the invention；Meanwhile any equivalent variations that all substantial technologicals according to the present invention do above-described embodiment
Change, modification and differentiation, still fall within protection scope of the present invention.
Claims (9)
1. the preparation method of a kind of amino and carboxyl-functional magnetic microsphere compound adsorbent, which is characterized in that including walking as follows
It is rapid:
S1, nanometer Fe3O4Preparation: under stirring condition, using ethylene glycol as solvent, 1:5:1.5 in mass ratio is sequentially added
FeCl3·6H2O, sodium acetate, Macrogol 4000 prepare nanometer Fe using hydro-thermal method after mixing3O4；
S2, amination nanometer Fe3O4Preparation: take nanometer Fe made from step S13O4It is dissolved in ethylene glycol, aminopropyl front three is added
Oxysilane flows back for 24 hours at 60-75 DEG C；Acquired solution is first washed, ethyl alcohol is washed again, be then dried to obtain amination nanometer
Fe3O4；The nanometer Fe3O4Solid-to-liquid ratio with aminopropyl trimethoxysilane is (0.5-1) g:1mL；
S3、Fe3O4The preparation of/GO composite material: by amination nanometer Fe3O4It is dissolved in ethylene glycol, being configured to mass concentration is
The solution A of 1.0mg/mL；Graphene oxide is dissolved in NaOH aqueous solution, and ultrasonic disperse 30min, being configured to mass concentration is
The B solution of 0.5mg/mL；By solution A and B solution, 1:1.5-2 is mixed by volume under mechanical stirring, continues to stir 2-3h；Institute
It obtains solution to be first washed with distilled water with ethanol washing, again, dry obtained Fe3O4/ GO composite material；
S4、Fe3O4/GO-NH2The preparation of/COOH compound adsorbent: Fe made from 0.1-0.5g step S3 is weighed3O4/ GO composite wood
Material is scattered in organic solvent, under stirring condition, methacrylic acid and acrylamide monomer is added, adds N, N- di-2-ethylhexylphosphine oxide
Acrylamide crosspolymer agent, potassium peroxydisulfate initiator, 60-80 DEG C of stirring in water bath 4-6h, after reaction, product is separated with magnet,
And it washes, drying to obtain Fe3O4/GO-NH2/ COOH compound adsorbent；The Fe3O4/ GO composite material and the metering system
The mass ratio of acid monomers be 1:10, the methacrylic acid, acrylamide monomer, N, N- methylene-bisacrylamide crosslinking agent,
The molar ratio of potassium peroxydisulfate is 1:0.8-1.5:2-5:2-3.
2. the preparation method of a kind of amino according to claim 1 and carboxyl-functional magnetic microsphere compound adsorbent,
It is characterized in that, methacrylic acid described in step S4, acrylamide monomer, N, N- methylene-bisacrylamide crosslinking agent, over cure
The molar ratio of sour potassium is 1:1.2:4:2.5.
3. the preparation method of a kind of amino according to claim 1 and carboxyl-functional magnetic microsphere compound adsorbent,
It is characterized in that, organic solvent described in step S4 is mixed by dehydrated alcohol and water according to volume ratio for 2:1.
4. the preparation method of a kind of amino according to claim 1 and carboxyl-functional magnetic microsphere compound adsorbent,
It is characterized in that, drying condition is dry 12h at 40 DEG C in step S4.
5. the preparation method of a kind of amino according to claim 1 and carboxyl-functional magnetic microsphere compound adsorbent,
It is characterized in that, hydrothermal reaction condition is 200 DEG C of reaction 10h in step S1.
6. the preparation method of a kind of amino according to claim 1 and carboxyl-functional magnetic microsphere compound adsorbent,
It is characterized in that, nanometer Fe described in step S23O4Solid-to-liquid ratio with aminopropyl trimethoxysilane is 1g:1mL.
7. the preparation method of a kind of amino according to claim 1 and carboxyl-functional magnetic microsphere compound adsorbent,
It is characterized in that, 1:1.8 is mixed by volume for solution A and B solution in step S3.
8. a kind of described in any item preparation methods of amino and carboxyl-functional magnetic microsphere compound adsorbent of claim 1 ~ 7
Compound adsorbent obtained is for the heavy metal ion in adsorbed water body.
9. the preparation method of a kind of amino according to claim 8 and carboxyl-functional magnetic microsphere compound adsorbent is made
Compound adsorbent for the metal copper ion in adsorbed water body.
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