CN105413659B - A kind of bionical adsorbent of magnetism and its application in the acid uranium-containing waste water of processing - Google Patents
A kind of bionical adsorbent of magnetism and its application in the acid uranium-containing waste water of processing Download PDFInfo
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- CN105413659B CN105413659B CN201510925238.XA CN201510925238A CN105413659B CN 105413659 B CN105413659 B CN 105413659B CN 201510925238 A CN201510925238 A CN 201510925238A CN 105413659 B CN105413659 B CN 105413659B
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 85
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003463 adsorbent Substances 0.000 title claims abstract description 77
- 230000005389 magnetism Effects 0.000 title claims abstract description 33
- 239000002253 acid Substances 0.000 title claims abstract description 27
- 239000002351 wastewater Substances 0.000 title claims abstract description 20
- 238000012545 processing Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 35
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 229920001690 polydopamine Polymers 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 9
- 239000007853 buffer solution Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 229960003638 dopamine Drugs 0.000 claims abstract description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- -1 dopamine hydrochlorides Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 4
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 4
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims description 3
- 229960004502 levodopa Drugs 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000010148 water-pollination Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- 235000013339 cereals Nutrition 0.000 description 8
- 239000013595 supernatant sample Substances 0.000 description 8
- XOIAVJBGSKXCKN-UHFFFAOYSA-N NC(=O)N.Cl.NO Chemical compound NC(=O)N.Cl.NO XOIAVJBGSKXCKN-UHFFFAOYSA-N 0.000 description 7
- 239000000872 buffer Substances 0.000 description 7
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000005375 photometry Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 231100000045 chemical toxicity Toxicity 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
-
- 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
- C02F2101/006—Radioactive compounds
-
- 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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Application the present invention relates to a kind of bionical adsorbent of magnetism and its in the acid uranium-containing waste water of processing.Improve the preparation Fe using PSSMA as surfactant3O4Solvent thermal process, realize uniform particle diameter, Fe can be synthesized on a large scale3O4Magnetic nanoparticle;Biomolecules of dopamine polymerize under trishydroxymethylaminomethane buffer system, and is coated on Fe3O4Magnetic nanoparticle surface builds the bionical adsorbent of novel magnetic with nucleocapsid.The bionical adsorbent of magnetism has good hydrophily and larger specific surface area because of the poly-dopamine structure of shell, there is very strong adsorption capacity in the abundant functional group in its surface to uranium in wider Acidity Range, it is big to the adsorption capacity of uranium, selectivity is good, and the uranium of adsorbent surface absorption can also use 0.1mol/L (NH4)2CO3Solution is easy to elute, and is conducive to recycle.
Description
Technical field
The invention belongs to uranium-containing waste water processing technology field, more particularly to the bionical adsorbent of a kind of magnetism and its in processing acid
Application in property uranium-containing waste water.
Background technology
In recent years, increasingly serious with fossil energy and environmental problem, nuclear energy is high as a kind of energy density, cleaning is low
The novel energy of carbon receives unprecedented attention and is rapidly developed.Wherein, uranium is as a kind of important strategic resource,
Important meaning is suffered to the development of the multiple fields such as national defence, agricultural, medicine, electric power.However, in uranium ore smelting and spentnuclear fuel
During post-processing, a large amount of uranium-bearing waste liquid is all inevitably had accumulated, the chemical toxicity due to uranium and interior illumination effect,
Potential radiological hazard is all constituted to mankind's activity and biotic environment.Therefore, it studies the processing of uranium in uranium-containing waste water and returns
Receiving method, utilization and recycle and environment decontamination to uranium ore resource have very important strategic importance.
Currently, the method for the acid uranium-containing waste water of processing mainly has:Ion-exchange, coprecipitation, solvent extraction, film point
From and absorption method.Wherein, absorption method is because of the advantage that its material source is wide, easy to operate, separative efficiency is high, secondary liquid waste is few, and by
It is widely used in the processing and recycling of acid uranium-containing waste water.Currently, common uranium absorption agent mainly has:Biomass, clay, ore
And composite nano materials, but the former is usually present the low problem of poor selectivity, adsorption capacity.Though and the nano materials such as mesoporous silicon
Have the advantages that large specific surface area, adsorption capacity are high, a variety of functional groups and extractant can be modified, but is followed in separation of solid and liquid, material
There is also the difficulties such as time-consuming, cumbersome, column pressure is higher for ring multiplexing etc., and the Chemical Decomposition method of magnetic auxiliary then can be very
Solve well problem above (Nunez.et al.Separation Science and Technology.1996,31 (10),
1393-1407)。
Composite magnetic has many advantages, such as that magnetic response signal is good, it is fast, economic and environment-friendly to be separated by solid-liquid separation, and has gradually been applied to
In the processing of the waste water containing Acidic Uranium, has many scholars in the recent period and relevant work is reported.Wang, et.al are reported
The magnetic mesoporous material (Wang.et.Al.Rsc.Adv.2014,4,32710-32717) and ion blotting method of amidoxime group modification
The magnetic composite (Wang.et.Al.Dalon Trans.2014,43,7050-7046) of preparation is to acid uranium-containing waste water
Processing method, the results showed that the material shows uranium preferably to adsorb point ability.But the shortcoming in similar work is magnetic
The long preparation period of property uranium absorption agent, consumes a large amount of organic solvent, easily causes secondary pollution and cost is higher.
Invention content
In view of the shortcomings of the prior art, the present invention provides a kind of bionical adsorbent of magnetism and its in the acid uranium-containing waste water of processing
In application.
A kind of bionical adsorbent of magnetism, is with Fe3O4Magnetic nanoparticle is core, using poly-dopamine as the core of shell
Shell structure adsorbent.
The grain size of the bionical adsorbent of magnetism is 200~300nm;Core Fe3O4Grain size be 190~220nm;Shell
Poly-dopamine thickness is 5~80nm.
A kind of preparation method of the bionical adsorbent of magnetism, includes the following steps:
(1) Iron(III) chloride hexahydrate, anhydrous sodium acetate are dissolved in ethylene glycol, and PSSMA (poly- (4- styrene is added
Sulfonic acid-copolymerization-maleic acid) sodium salt) it is used as surfactant, it stirs evenly, 200 DEG C of reactions 8~10h, prepared Fe3O4It is micro-
After ball cooling, 12h is dried in vacuo at ethyl alcohol and deionized water alternately washing 4~5 times, 35 DEG C, be made grain size be 190~
The Fe of 220nm3O4Magnetic Nano microsphere;
(2) by Fe3O4It is scattered in trishydroxymethylaminomethane buffer solution, solvent is ethanol/water solution, is slowly added to
The ethanol/water solution of dopamine hydrochloride, control temperature of reaction system are 25 DEG C, the lower reaction of lasting stirring 2.5~for 24 hours;Magnet
It after detaching product, is alternately washed 3~4 times with deionized water and ethyl alcohol, 12h is dried in vacuo at 45 DEG C, magnetic bionical adsorbent is made.
In reaction system in step (1), each component mass ratio is:Iron(III) chloride hexahydrate:PSSMA:Anhydrous sodium acetate:
Ethylene glycol=(0.95~1.05):(0.95~1.05):(2.9~3.1):(44~46).
In step (2), the pH of the buffer solution is 8.48~8.52, is adjusted by the hydrochloric acid of 0.5mol/L, molten
The volume ratio of second alcohol and water is 1 in agent ethanol/water solution:(1~10), preferred volume ratio 1:(1~2.5), dosage 2.6g
Trishydroxymethylaminomethane is per 1g Fe3O4;The volume of second alcohol and water in the solvent of the ethanol/water solution of the dopamine hydrochloride
Than being 1:(1~10), preferred volume ratio 1:(1~2.5), addition are 1.9~2.1g dopamine hydrochlorides per 1g Fe3O4。
A kind of application of the bionical adsorbent of magnetism in the acid uranium-containing waste water of processing, the bionical adsorbent of magnetism is by very
It after sky is dry, is added in reaction bulb, the acid uranium-bearing aqueous solution of addition, after ultrasonic 10min, in 25 ± 0.2 DEG C of constant temperature
Under vibrated to adsorption equilibrium with 240r/min;
Acid uranium containing water pH value of solution=1~6.5, wherein a concentration of 95~105mg/L of uranium.
Acid uranium-bearing aqueous solution described in 25mL is often handled, the bionical adsorbent of magnetism of required addition is 0.025~0.25g;
The amount of preferred adsorbent is 0.025~0.1g.
The uranium of the bionical adsorbent surface absorption of magnetism, uses 0.1mol/L under 25 ± 0.2 DEG C of constant temperature
(NH4)2CO3Solution stripping is attached, and realizes recycling.
Adsorbent preparation principle:It is not explained explicitly about the mechanism of polymerization of poly-dopamine at present, but it is mainly logical
The polymerization for crossing dopamine itself is oxidized to a kind of jade, it is poly- that a kind of jade formula is overlapped mutually realization under weakly alkaline environment by phenolic hydroxyl group
It closes, poly-dopamine is in Fe3O4The outer hydrogen bond action or physics by between hydroxyl of magnetic Nano microsphere is deposited as poly- DOPA in the form of accumulating
Amine layer is not related to the coordination with Fe elements.
Absorption principle:Absorption for uranium, the present invention is the study found that the mainly a large amount of hydroxyl of poly-dopamine shell is made
With amino is primarily involved in phenyl ring cyclization, and only part amino takes part in the effect with uranium.
Beneficial effects of the present invention are:
1) present invention by biomolecules of dopamine in trishydroxymethylaminomethane buffer system (pH=8.48~8.52)
Under polymerization, be combined with magnetic Nano material, build with nucleocapsid the bionical adsorbent of novel magnetic, prepare
Novelty simple for process, it is easy to operate, the long preparation period of conventional magnetic uranium absorption agent is avoided, organic solvent largely consumes and life
Disadvantage of high cost is produced, the cost of actual motion is reduced, it is economic and environment-friendly.
2) present invention improves the preparation Fe using PSSMA as surfactant3O4Solvent thermal process, it is equal to realize grain size
One, the Fe with superparamagnetism3O4Nano particle synthesizes on a large scale, is conducive to industry amplification and applies.
3) the bionical adsorbent of magnetism prepared by the present invention have because of the poly-dopamine structure of shell good hydrophily with
Larger specific surface area, there is very strong adsorption capacity in the abundant functional group in surface to uranium in wider Acidity Range, right
The adsorption capacity of uranium is big, and selectivity is good, in the 100mg/L of pH >=5 contains uranium solution, has reached 50mg/g to the adsorption capacity of uranium
More than, removal rate can reach 90% or more.
4) the bionical adsorbent of magnetism prepared by the present invention has good magnetic responsiveness, by external magnetic field, can hold very much
It is easily separated to go out to capture the sorbent material of uranium, the period of separation of solid and liquid and material circulation multiplexing is shortened, putting is greatly reduced
The cost of operation;And the uranium of adsorbent surface absorption can also use 0.1mol/L (NH4)2CO3Solution is easy to elute, and washes
De- rate reaches 95% or more, is conducive to recycle.
Description of the drawings
Fig. 1 is the X-ray diffraction spectrogram of magnetic bionical adsorbent in embodiment 1;Wherein, (a) is Fe3O4Magnetic Nano
The X-ray diffraction spectrogram of grain;(b) it is the Fe of poly-dopamine modification3O4The X-ray diffraction spectrogram of magnetic nanoparticle.
Fig. 2 is the transmission electron microscope photo of magnetic bionical adsorbent in embodiment 1;Wherein, (a) is Fe3O4Magnetism is received
The transmission electron microscope photo of rice grain;(b) it is the Fe of poly-dopamine modification3O4Magnetic nanoparticle (magnetic bionical adsorbent) it is saturating
Penetrate electromicroscopic photograph.
Fig. 3 is the influence schematic diagram that the acid pH value containing uranium solution removes magnetic bionical adsorbent uranium efficiency.
Specific implementation mode
The present invention will be further described with reference to the accompanying drawings and detailed description.It is emphasized that following the description
It is only exemplary, the range being not intended to be limiting of the invention and its application.
Embodiment 1:A kind of fast synthesis method of the bionical adsorbent of magnetism
(1) 1.00g PSSMA are added into the ethylene glycol of 40mL, heating stirring to dissolving;It sequentially adds at room temperature
1.08g Iron(III) chloride hexahydrates, 3.00g anhydrous sodium acetates, after continuing stirring and dissolving 1h, the tetrafluoroethene for being transferred to 200mL is anti-
It answers in kettle, heating reaction 10h at 200 DEG C, taking-up reaction kettle, after cool overnight, prepared Fe is poured out from kettle3O4Microballoon is used
Ethyl alcohol and deionized water are dried in vacuo 12h at alternately washing 4~5 times, 35 DEG C, and Fe is made3O4Magnetic nanoparticle;
(2) trishydroxymethylaminomethane buffer solution is prepared, solvent is that volume ratio is 1:1 ethanol/water mixed solution, with
The hydrochloric acid solution of 0.5mol/L adjusts pH=8.5;At 25 DEG C, by Fe obtained in step (1)3O40.1g points of magnetic nanoparticle
It dissipates in 90mL buffer solutions, ultrasonic 10min, under mechanical agitation, is slowly added to dopamine hydrochloride solution, the DOPA amine salt
Acid salt solution is the mixed solution that 0.2g dopamine hydrochlorides are dissolved in 5mL ethyl alcohol and 5mL water, continues mechanic whirl-nett reaction 5h;System
The magnetism bionical adsorbent for obtaining poly-dopamine cladding after magnet detaches product, is alternately washed at 3~4 times, 45 DEG C very with water and ethyl alcohol
The dry 12h of sky.
Fig. 1 is the X-ray diffraction spectrogram of magnetic bionical adsorbent, and (a) show the Fe prepared in step (1)3O4Magnetism is received
The X-ray diffraction spectrogram of meter Wei Qiu (b) show the X-ray diffraction spectrogram of the bionical adsorbent of magnetism with nucleocapsid.Spectrum
Scheme crystal face (111) corresponding in (a), (b), (220), (311), (400), (422), (511), (440) belong to standard Fe3O4
The centroid cubic crystal system of card, this illustrates that the bionical adsorbent of magnetism after modification poly-dopamine shell does not change original Fe3O4
Crystal structure.
Fig. 2 is the transmission electron microscope photo of magnetic bionical adsorbent, and (a) show the Fe prepared in step (1)3O4
Magnetic Nano microsphere, grain size is 190~220nm, and average grain diameter is 200nm;(b) it show the Fe of poly-dopamine modification3O4Magnetic
Property nano particle, core (color deeper portion) be Fe3O4Magnetic nanoparticle, average grain diameter 200nm, outer layer (canescence portion
Point) it is the poly-dopamine shell modified, average thickness 20nm.
Embodiment 2:Application of the magnetic bionical adsorbent in the acid uranium-containing waste water of processing
The uranium solution 25mL of a concentration of 100mg/L is pipetted in conical flask, with 1mol/L HNO3Or the NaOH of 1mol/L is molten
It is 3.0 that liquid, which adjusts its pH, after the magnetism bionical adsorbent 0.05g, ultrasonic 10min of 1 gained of embodiment is added, at 25 ± 0.2 DEG C
Constant temperature air bath in 240r/min vibrate 72h.After magnet separating adsorbent, supernatant samples are taken out, in water sample to be measured
In sequentially add 1mol/L tartaric acid buffer, hydroxylamine hydrochloride-urea liquid and azo arsenic III indicator and constant volume, with point
Light photometry measures the mass concentration of uranium in solution, and removal rate E=of the adsorbent to uranium is calculated according to adsorption equilibrium formula
8.1%.
Embodiment 3:Application of the magnetic bionical adsorbent in the acid uranium-containing waste water of processing
The uranium solution 25mL of a concentration of 100mg/L is pipetted in conical flask, with 1mol/L HNO3Or the NaOH of 1mol/L is molten
It is 3.5 that liquid, which adjusts its pH, after the magnetism bionical adsorbent 0.05g, ultrasonic 10min of 1 gained of embodiment is added, at 25 ± 0.2 DEG C
Constant temperature air bath in 240r/min vibrate 72h.After magnet separating adsorbent, supernatant samples are taken out, in water sample to be measured
In sequentially add 1mol/L tartaric acid buffer, hydroxylamine hydrochloride-urea liquid and azo arsenic III indicator and constant volume, with point
Light photometry measures the mass concentration of uranium in solution, and removal rate E=of the adsorbent to uranium is calculated according to adsorption equilibrium formula
22.3%.
Embodiment 4:Application of the magnetic bionical adsorbent in the acid uranium-containing waste water of processing
The uranium solution 25mL of a concentration of 100mg/L is pipetted in conical flask, with 1mol/L HNO3It is molten with the NaOH of 1mol/L
It is 4.0 that liquid, which adjusts its pH, after the magnetism bionical adsorbent 0.05g, ultrasonic 10min of 1 gained of embodiment is added, at 25 ± 0.2 DEG C
Constant temperature air bath in 240r/min vibrate 72h.After magnet separating adsorbent, supernatant samples are taken out, in water sample to be measured
In sequentially add 1mol/L tartaric acid buffer, hydroxylamine hydrochloride-urea liquid and azo arsenic III indicator and constant volume, with point
Light photometry measures the mass concentration of uranium in solution, and removal rate E=of the adsorbent to uranium is calculated according to adsorption equilibrium formula
23.5%.
Embodiment 5:Application of the magnetic bionical adsorbent in the acid uranium-containing waste water of processing
The uranium solution 25mL of a concentration of 100mg/L is pipetted in conical flask, with 1mol/L HNO3It is molten with the NaOH of 1mol/L
It is 4.5 that liquid, which adjusts its pH, after the magnetism bionical adsorbent 0.05g, ultrasonic 10min of 1 gained of embodiment is added, at 25 ± 0.2 DEG C
Constant temperature air bath in 240r/min vibrate 72h.After magnet separating adsorbent, supernatant samples are taken out, in water sample to be measured
In sequentially add 1mol/L tartaric acid buffer, hydroxylamine hydrochloride-urea liquid and azo arsenic III indicator and constant volume, with point
Light photometry measures the mass concentration of uranium in solution, and removal rate E=of the adsorbent to uranium is calculated according to adsorption equilibrium formula
31.4%.
Embodiment 6:Application of the magnetic bionical adsorbent in the acid uranium-containing waste water of processing
The uranium solution 25mL of a concentration of 100mg/L is pipetted in conical flask, with 1mol/L HNO3It is molten with the NaOH of 1mol/L
It is 5.0 that liquid, which adjusts its pH, after the magnetism bionical adsorbent 0.05g, ultrasonic 10min of 1 gained of embodiment is added, at 25 ± 0.2 DEG C
Constant temperature air bath in 240r/min vibrate 72h.After magnet separating adsorbent, supernatant samples are taken out, in water sample to be measured
In sequentially add 1mol/L tartaric acid buffer, hydroxylamine hydrochloride-urea liquid and azo arsenic III indicator and constant volume, with point
Light photometry measures the mass concentration of uranium in solution, and removal rate E=of the adsorbent to uranium is calculated according to adsorption equilibrium formula
90.5%.
Embodiment 7:Application of the magnetic bionical adsorbent in the acid uranium-containing waste water of processing
The uranium solution 25mL of a concentration of 100mg/L is pipetted in conical flask, with 1mol/L HNO3It is molten with the NaOH of 1mol/L
It is 5.5 that liquid, which adjusts its pH, after the magnetism bionical adsorbent 0.05g, ultrasonic 10min of 1 gained of embodiment is added, at 25 ± 0.2 DEG C
Constant temperature air bath in 240r/min vibrate 72h.After magnet separating adsorbent, supernatant samples are taken out, in water sample to be measured
In sequentially add 1mol/L tartaric acid buffer, hydroxylamine hydrochloride-urea liquid and azo arsenic III indicator and constant volume, with point
Light photometry measures the mass concentration of uranium in solution, and removal rate E=of the adsorbent to uranium is calculated according to adsorption equilibrium formula
91.3%.
Embodiment 8:Application of the magnetic bionical adsorbent in the acid uranium-containing waste water of processing
The uranium solution 25mL of a concentration of 100mg/L is pipetted in conical flask, with 1mol/L HNO3It is molten with the NaOH of 1mol/L
It is 6.0 that liquid, which adjusts its pH, after the magnetism bionical adsorbent 0.05g, ultrasonic 10min of 1 gained of embodiment is added, at 25 ± 0.2 DEG C
Constant temperature air bath in 240r/min vibrate 72h.After magnet separating adsorbent, supernatant samples are taken out, in water sample to be measured
In sequentially add 1mol/L tartaric acid buffer, hydroxylamine hydrochloride-urea liquid and azo arsenic III indicator and constant volume, with point
Light photometry measures the mass concentration of uranium in solution, and removal rate E=of the adsorbent to uranium is calculated according to adsorption equilibrium formula
97.3%.
Fig. 3 show the influence that the acid pH value containing uranium solution removes magnetic bionical adsorbent uranium efficiency, in pH >=5
100mg/L acidity contains in uranium solution, and magnetic bionical adsorbent has reached 50mg/g or more to the adsorption capacity of uranium, and removal rate reaches
90% or more.
Embodiment 9:The regeneration of magnetic bionical adsorbent with recycle
Select 0.1mol/L (NH4)2CO3Strippant of the solution as uranium reaches the magnetism after adsorption equilibrium in embodiment 6
Bionical adsorbent is washed with deionized 4~5 times after magnet detaches, to remove the unadsorbed uranium solution in surface, 60 DEG C of vacuum
After dry 12h, it is transferred in conical flask, and the 0.1mol/L (NH of 25mL are added4)2CO3Solution, it is empty in 25 ± 0.2 DEG C of constant temperature
8h is vibrated with 240r/min in gas bath, after magnet detaches solid, supernatant samples is taken out, uses inductively-coupled plasma spectrometer
(ICP-OES) mass concentration of uranium is measured, the eluting rate that uranium is calculated according to adsorption equilibrium formula reaches 96%, as shown in table 1, magnetic
Property bionical sorbent circulation be multiplexed 3 times after, absorption property is without being substantially reduced.
The recycling performance of the magnetic bionical adsorbent adsorption uranium of table 1
Claims (5)
1. a kind of bionical adsorbent of magnetism for adsorption uranium, which is characterized in that the bionical adsorbent of magnetism, is with Fe3O4Magnetic
Property nano particle be core, using poly-dopamine as the nucleocapsid adsorbent of shell;The grain size of magnetic bionical adsorbent is 200~
300nm, core Fe3O4Grain size be 190~220nm, shell poly-dopamine thickness be 20~80nm;
The preparation method of the bionical adsorbent of magnetism includes the following steps:
(1) Iron(III) chloride hexahydrate, anhydrous sodium acetate are dissolved in ethylene glycol, and PSSMA is added as surfactant, stirred
It mixes uniformly, 200 DEG C of reactions 8~10h, prepared Fe3O4After microballoon cooling, alternately washed 4~5 times with ethyl alcohol and deionized water,
It is dried in vacuo 12h at 35 DEG C, the Fe that grain size is 190~220nm is made3O4Magnetic nanoparticle;
(2) by Fe3O4It is scattered in trishydroxymethylaminomethane buffer solution, solvent is ethanol/water solution, is slowly added to DOPA
The ethanol/water solution of amine hydrochlorate, control temperature of reaction system are 25 DEG C, the lower reaction of lasting stirring 2.5~for 24 hours;Magnet detaches
It after product, is alternately washed 3~4 times with deionized water and ethyl alcohol, 12h is dried in vacuo at 45 DEG C, magnetic bionical adsorbent is made;
In step (2), the pH of the buffer solution is 8.48~8.52, is adjusted by the hydrochloric acid of 0.5mol/L, solvent second
The volume ratio of second alcohol and water is 1 in alcohol/aqueous solution:(1~10), dosage are 2.6g trishydroxymethylaminomethanes per 1g Fe3O4;Institute
The volume ratio for stating second alcohol and water in the solvent of the ethanol/water solution of dopamine hydrochloride is 1:(1~10), addition be 1.9~
2.1g dopamine hydrochlorides are per 1g Fe3O4;
In reaction system in step (1), each component mass ratio is:Iron(III) chloride hexahydrate:PSSMA:Anhydrous sodium acetate:Second two
Alcohol=(0.95~1.05):(0.95~1.05):(2.9~3.1):(44~46).
2. a kind of application of the bionical adsorbent of magnetism described in claim 1 in the acid uranium-containing waste water of processing, which is characterized in that institute
Magnetic bionical adsorbent is stated after vacuum drying, is added in reaction bulb, is added acid uranium-bearing aqueous solution, after ultrasonic 10min,
It is vibrated to adsorption equilibrium with 240r/min under 25 ± 0.2 DEG C of constant temperature;
The uranium of magnetic bionical adsorbent surface absorption, uses 0.1mol/L (NH under 25 ± 0.2 DEG C of constant temperature4)2CO3It is molten
Lyolysis is adsorbed, and can realize recycling.
3. application according to claim 2, which is characterized in that acid uranium containing water pH value of solution=1~6.5, wherein
A concentration of 95~105mg/L of uranium.
4. application according to claim 2, which is characterized in that acid uranium-bearing aqueous solution described in 25mL is often handled, it is required to add
The bionical adsorbent of magnetism entered is 0.025~0.25g.
5. application according to claim 2, which is characterized in that acid uranium-bearing aqueous solution described in 25mL is often handled, it is required to add
The bionical adsorbent of magnetism entered is 0.025~0.1g.
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