CN104549127B - Magnetic coupling hydroxyapatite nano particulate and its preparation method and application - Google Patents

Magnetic coupling hydroxyapatite nano particulate and its preparation method and application Download PDF

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CN104549127B
CN104549127B CN201510044086.2A CN201510044086A CN104549127B CN 104549127 B CN104549127 B CN 104549127B CN 201510044086 A CN201510044086 A CN 201510044086A CN 104549127 B CN104549127 B CN 104549127B
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hydroxyapatite
magnetic coupling
magnetic
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nano particle
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CN104549127A (en
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谭瑞琴
庄福强
岳燕丽
宋伟杰
黄琦金
许炜
张贤鹏
徐峰
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Ningbo University
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    • 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
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character

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Abstract

The invention discloses a kind of magnetic coupling hydroxyapatite nano particulate, by Fe3O4Nano particle is constituted with hydroxyapatite nanoparticle, Fe3O4Mol ratio with hydroxyapatite is（1‑10）:1, the magnetic coupling hydroxyapatite nano particulate is Fe3O4Nano particle and the uniform spherical agglomeration thing or granule for distributing alternately of hydroxyapatite nanoparticle.The preparation method of magnetic coupling hydroxyapatite nano particulate of the present invention is simple, heavy metal ions in sewage and treatment later stage can efficiently be removed can realize that rapid magnetic is separated, to the adsorbance of lead ion in sewage up to 440 mg/g, the adsorbance of cadmium ion is up to 238 mg/g,, up to 139 mg/g, the adsorbance of copper ion is up to 135 mg/g for the adsorbance of zinc ion；Magnetic coupling hydroxyapatite nano particulate of the invention has quick magnetic response characteristic, and externally-applied magnetic field can just realize quick separation of solid and liquid, and separative efficiency is high, simple to operate, efficient, the noresidue in water body, will not cause secondary pollution to water body and environment.

Description

Magnetic coupling hydroxyapatite nano particulate and its preparation method and application
Technical field
The present invention relates to technical field of material, and in particular to a kind of magnetic coupling hydroxyapatite nano particulate and its Preparation method and application.
Background technology
Battery manufacturing industry, metal smelt, mining etc. one is have stimulated the need for the development of modern economy and industrial production big Highly energy-consuming, the extensive development of high pollution enterprise are criticized, substantial amounts of heavy metal ion is contained in the waste water that these enterprises produce, it is poisonous Ion flows into river, river with the waste water that enterprise discharges, and gos deep into underground water, heavy damage ecological environment.Therefore heavy metal pollution is solved Problem, the ecological environment of protection human survival has turned into the problem of countries in the world urgent need to resolve.
Hydroxyapatite is common a kind of material in current Industrial Waste Water Treatments, for the removal of heavy metal in sewage. Native hydroxyl apatite is cheap and easy to get, with certain wastewater treatment efficiency, for example, reachable to the adsorbance of lead ion 28.6mg/g；Artificial synthesized big compared with pure, specific surface area, nano level hydroxyapatite can significantly improve a huge sum of money in sewage Belong to the removal capacity of ion, the pattern depending on synthetic product is different, be 260-416mg/g to the adsorbance of lead ion, but hydroxyl phosphorus Lime stone is general with powdered presence, there is separation of solid and liquid difficulty, the low defect of the rate of settling in the Industrial Waste Water Treatments later stage, one Determine to increase in degree the cost of commercial Application, the hydroxyapatite remained in water body after use has one to microorganisms in water Fixed toxic and side effect.
Magnetic separation technique starts to be applied to engineering of water treatment currently as an emerging technology, and magnetic separation technique is by magnetic A kind of effect of field force, physical separation method that the material different to magnetic is separate is processing the heavy metal ion later stage, outward Plus magnetic field quickly can separate from the aqueous solution, so as to overcome adsorbent to reclaim difficult defect, it is to avoid nano adsorber is to micro- The toxic and side effect of biological and human body.Combined with hydroxyapatite about magnetic Nano material and reported less, such as CN 103541005A A kind of preparation method of magnetic hydroxylapatite crystal whisker ball is disclosed, the method is repaiied with soluble calcium salt, soluble microcosmic salt, bilayer The nano ferriferrous oxide ferrofluid of decorations is raw material, and urea is to prepare magnetic hydroxyl under acidity-basicity regulator, water bath condition Apatite whiskers ball, can be used for the fields such as target medicine carrier, biological engineering material, but used in the method experimentation Nano ferriferrous oxide needs to be modified by double-deck, and this increased the complexity of method to a certain extent, and to modify four oxygen Change the coating material generally more difficult removal added by three-iron, this also increases the complexity of production to a certain extent. H.Yang,S.Masse,H.Zhang,C.Hélary,L.Li,T.Coradin,Surface reactivity of hydroxyapatite nanocoatings deposited on iron oxide magnetic spheres toward toxic metals,J.Colloid Inter.Sci.417(2014)The Fe of 1-8. reports3O4@HydroxyapatiteIt is compound micro- Ball and for lead ion removal, needed to use in this composite particles building-up process aspartic acid process carry out surface be modified, Building-up process is complicated.Liao,D.；Zheng,W.；Li,X.；Yang,Q.；Yue,X.；Guo,L.；Zeng,G.Removal of lead(II)from aqueous solutions using carbonate hydroxyapatite extracted from The Li Dengxiao of eggshell waste.J.Hazard.Mater.2010,177 (1-3), 126-130. report are using discarded Egg shell synthesized magnetic calcium hydroxy phosphate composite for lead ion removal, but this material scatter difference is to lead The removal effect of ion is limited.CN102500333A propose with natural zeolite, hydroxyapatite, ferroso-ferric oxide, shitosan and Cationic surfactant prepares a kind of magnetic cationic surfactant modified chitosan/hydroxy-apatite as stock Stone/zeolite composition, as magnetic organic/inorganic composite material adsorbent, and this adsorbent can be applied to rotten in water removal The heavy metal contaminants such as the organic pollution such as sour, Congo red and copper ion are grown, but the material prepares raw material complexity, to treatment The pH value of sewage is required, and needs to adjust the pH value of sewage to partial neutral (6.0-7.0) before treatment, and operability is poor, and Absorption property is not (, in 80mg/kg, cupric ion adsorption is in 27mg/kg for humic acid and Congo red adsorbance) high, and this is in certain journey Its application in sewage disposal is limited on degree.
The content of the invention
The technical problems to be solved by the invention are：In view of the shortcomings of the prior art, there is provided a kind of magnetic coupling hydroxyl phosphorus Lime stone nanoparticle, its preparation method is simple, easily operated, can be applied to process heavy metal wastewater thereby；The nanoparticle has excellent Different acid resistance, also almost without Iron pick up in the case of pH=1.0-3.0, the nanoparticle is applied to the various pH for the treatment of The heavy metal wastewater thereby of value, can efficiently remove heavy metal ions in sewage and treatment later stage can realize that rapid magnetic is separated.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：Magnetic coupling hydroxyapatite nano particulate, By Fe3O4Nano particle is constituted with hydroxyapatite nanoparticle, Fe3O4It is (1-10) with the mol ratio of hydroxyapatite:1, should Magnetic coupling hydroxyapatite nano particulate is Fe3O4Nano particle and the uniform ball for distributing alternately of hydroxyapatite nanoparticle Shape aggregate or granule.
The preparation method of magnetic coupling hydroxyapatite nano particulate, comprises the following steps：
1) under nitrogen protection atmosphere, by soluble trivalent iron salt with soluble divalent iron salt with (1.9-2.2):1 rubs You form mixture than well mixed, then the mixture are dissolved in deionized water with the ratio of 0.5-0.7g/mL, mechanical agitation After 10-30min, to ammoniacal liquor is added dropwise in solution, until the color blackening of solution, magnetic point is carried out after continuing mechanical agitation 0.5-1h From magnetisable material, then magnetisable material deionized water and absolute ethyl alcohol cyclic washing to obtaining being obtained, then in vacuum condition Under dry 1-6h in 45-80 DEG C, obtain the Fe of black3O4Nano particle；
2) Fe that will be prepared3O4Nano particle, soluble calcium salt and lauryl sodium sulfate are according to 1:(1-10):1 Mixed in molar ratio is formed uniformly mixture, then the mixture is dissolved in deionized water with the ratio of 0.8-2.5g/mL, and machinery is stirred 10-30min is mixed, the Na with above-mentioned soluble calcium salt equimolar concentration is then added in the solution2CO3, machinery is continued at room temperature Magnetic Isolation is carried out after stirring 1-3h, magnetisable material is obtained, then magnetisable material deionized water and absolute ethyl alcohol to obtaining is anti- After backwashing is washed, and then dries 1-6h in 45-80 DEG C under vacuum, obtains Fe3O4/CaCO3Nano particle presoma；
3) Fe that will be prepared3O4/CaCO3Nano particle presoma dissolves in the Na that concentration is 0.15-0.3mol/L3PO4 In the aqueous solution, uniform solution is obtained through sonic oscillation, solution is then transferred to autoclave, in 150-300 DEG C of condition After lower hydro-thermal reaction 3-24h, room temperature is cooled to, product is washed repeatedly, alcohol is washed, finally Magnetic Isolation, vacuum drying again Magnetic coupling hydroxyapatite nano particulate is obtained afterwards, and its form is Fe3O4Nano particle is equal with hydroxyapatite nanoparticle The even spherical agglomeration thing or granule for distributing alternately, Fe3O4It is (1-10) with the mol ratio of hydroxyapatite:1.
Lauryl sodium sulfate (abbreviation SDS) is a kind of surfactant, as a kind of anion surfactant, is had Certain critical micelle concentration, when the critical micelle concentration more than this surfactant, this anion surfactant Microballoon micelle easily is agglomerated into, due to the interaction between surfactant and calcium ion, this microballoon micelle is in calcium carbonate Play a part of to promote calcium carbonate granule nucleation, grow and be agglomerated into big particle in Crystallization, in addition four under mechanical agitation Fe 3 O nano particle can be uniformly embedded into the space between calcium carbonate granule.
Preferably, step 1) described in soluble trivalent iron salt be FeCl3、FeCl3·6H2O、Fe(NO3)3·9H2O And Fe2(SO4)3In one or more, described soluble divalent iron salt is FeCl2、FeCl2·4H2O and FeSO4·7H2In O One or more.
Preferably, step 2) described in soluble calcium salt be CaCl2With Ca (NO3)2In one or two.
Application of the magnetic coupling hydroxyapatite nano particulate of the invention in heavy metal wastewater thereby is processed.Magnetic of the invention Property composite hydroxylapatite nanoparticle there is excellent acid resistance, in the case of pH value=1.0-3.0 also almost without iron from Son is separated out, and can efficiently remove the Pb in sewage2+、Cd2+、Zn2+、Cu2+Etc. heavy metal ion and treatment the later stage can realize quick magnetic Property separate, using permanent magnet can in short time (in such as 1 minute) effectively Magnetic Isolation, separative efficiency up to more than 98%, Noresidue in water body.For the sewage of the different pH value containing heavy metal ion, magnetic coupling hydroxyapatite of the invention is received The adsorption mechanism of rice particulate heavy metal ion is different.With magnetic coupling hydroxyapatite nano particulate pair of the invention Pb2+Absorption as a example by, during pH value=3-6, with ion exchange with absorption complex mechanism based on, its reaction equation is：
Ca10(PO4)6(OH)2+xPb2+→xCa2++Ca10-xPbx(PO4)6(OH)2
As pH value=1-3, predominantly dissolving-PRECIPITATION MECHANISM, the reaction equation of course of dissolution is：
nCa10(PO4)6(OH)2+4mH+→10nCa2++3mHPO4 2-+(2n-m)(PO4)3(OH)10-+mH2O
The reaction equation of precipitation process is：
(x+5y)Pb2++xHPO4 2-+y(PO4)3(OH)10-→xPbHPO4+yPb5(PO4)3(OH)
Either which kind of adsorption mechanism, adsorbance higher is respectively provided with to heavy metal ions in sewage, adsorbs the network for being formed Compound or sediment, the phase can be by Magnetic Isolation and Fe after treatment3O4Quickly and easily separated from water body together, separated Efficiency high, the noresidue in water body will not be polluted to water body and environment.Therefore, magnetic coupling hydroxy-apatite of the invention When stone nanoparticle is applied to waste water control, do not limited by pH value of sewage water, before processing need not be pre-adjusted the pH value of sewage, fitted It is wide with scope, it is applicable to the heavy metal wastewater thereby of various pH value.
Compared with prior art, the advantage of the invention is that：The inventive method is in Fe3O4/CaCO3Nano particle presoma Preparation process in the organic solvent such as ethylene glycol, isopropanol is not used, because organic solvent can increase cost, and organic solvent has There is certain toxicity；The Fe of synthesis3O4Nano particle need not be modified its surface in use, Fe3O4In conduct The lauryl sodium sulfate effect of surfactant it is lower can and CaCO3Form the uniform spherical agglomeration thing for distributing alternately or group Granular Fe3O4/CaCO3Nano particle presoma, the Fe3O4/CaCO3Nano particle presoma can be prepared using hydrothermal method Magnetic coupling hydroxyapatite nano particulate, preparation method is simple；Magnetic coupling hydroxyapatite nano particulate of the invention is Fe3O4Nano particle and the uniform spherical agglomeration thing for distributing alternately of hydroxyapatite nanoparticle or pellet shape monodispersity Grain, with excellent acid resistance, also almost without Iron pick up in the case of pH value=1.0-3.0；Magnetic of the invention is answered Close the heavy metal wastewater thereby that hydroxyapatite nano particulate is applied to the various pH value for the treatment of, can efficiently remove in sewage heavy metal from The son and treatment later stage can realize that rapid magnetic is separated, to the adsorbance of lead ion in sewage up to 440mg/g, the absorption of cadmium ion , up to 238mg/g, up to 139mg/g, the adsorbance of copper ion is up to 135mg/g for the adsorbance of zinc ion for amount；It is compared to non- The simple hydroxyapatite of magnetic, magnetic coupling hydroxyapatite nano particulate of the present invention has quick magnetic response characteristic, outward Plus magnetic field can just realize quick separation of solid and liquid, separative efficiency is high, simple to operate, efficient, and the noresidue in water body will not be to water Body and environment cause secondary pollution.
Brief description of the drawings
Fig. 1 is Fe prepared by embodiment 13O4Nano particle (#2), Fe3O4/CaCO3Nano particle presoma (#1) and magnetic The XRD comparison diagrams of composite hydroxylapatite nanoparticle (#3)；
Fig. 2 a are Fe prepared by embodiment 23O4The SEM figures of nano particle；
Fig. 2 b are Fe prepared by embodiment 23O4/CaCO3The SEM figures of nano particle presoma；
Fig. 2 c are the SEM figures of magnetic coupling hydroxyapatite nano particulate prepared by embodiment 2；
Fig. 3 is the magnetic coupling hydroxyapatite nano particulate for preparing of embodiment 1 at various ph values to Pb2+Consolidate Qualitative energy, the Ca to separating out2+Concentration and the Ca to being separated out in the aqueous solution containing lead ion2+The curve map of concentration.
Specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
The preparation method of the magnetic coupling hydroxyapatite nano particulate of embodiment 1, is carried out in accordance with the following steps：
1) under nitrogen protection atmosphere, by the FeCl of 0.85g3·6H2The FeCl of O and 0.30g2·4H2O is well mixed shape Resulting mixture, then the mixture is dissolved in 200mL deionized waters, after mechanical agitation 30min, to being added dropwise over ammonia in solution Water, until the color blackening of solution, Magnetic Isolation is carried out after continuing mechanical agitation 1h, obtains magnetisable material, then the magnetic to obtaining Property material deionized water and absolute ethyl alcohol cyclic washing, then dry 6h in 45 DEG C under vacuum, obtain 0.46g black Fe3O4Nano particle；
2) Fe of the 0.46g that will be prepared3O4The CaCl of nano particle, 0.89g2With the lauryl sodium sulfate of 1.15g It is well mixed to form mixture, then the mixture is dissolved in 120mL deionized waters, mechanical agitation 30min, then in the solution The Na for adding 40mL to contain 0.85g2CO3The aqueous solution, carry out Magnetic Isolation after continuing mechanical agitation 3h at room temperature, obtain magnetic Property material, then magnetisable material deionized water and absolute ethyl alcohol cyclic washing to obtaining, then under vacuum in 45 DEG C 6h is dried, the Fe of 0.75g is obtained3O4/CaCO3Nano particle presoma；
3) Fe of the 0.75g that will be prepared3O4/CaCO3Nano particle presoma dissolves in 70mL concentration for 0.15mol/L Na3PO4In the aqueous solution, uniform solution is obtained through sonic oscillation, solution is then transferred to 100mL autoclaves, Under the conditions of 180 DEG C after hydro-thermal reaction 3h, room temperature is cooled to, product is washed repeatedly, alcohol is washed, finally Magnetic Isolation again, very Sky obtains the magnetic coupling hydroxyapatite nano particulate of embodiment 1 after drying, its form is Fe3O4Nano particle and hydroxyl Spherical agglomeration thing or granule that apatite nano particle uniformly distributes alternately, Fe3O4It is 5 with the mol ratio of hydroxyapatite:2.
Fig. 1 is the Fe that embodiment 1 is prepared3O4Nano particle (#2), Fe3O4/CaCO3Nano particle presoma (#1) and The XRD comparison diagrams of magnetic coupling hydroxyapatite nano particulate (#3), as can be seen from Figure 1 magnetic coupling hydroxyapatite nano It is existing in particulate to belong to Fe3O4Phase：(220), also there is the phase for belonging to hydroxyapatite (311), (400), (511), (440)： (002), (211), (300), (202), (130), (222), (213), and Fe3O4/CaCO3Nano particle presoma is anti-through hydro-thermal Magnetic coupling hydroxyapatite nano particulate has been fully converted into after answering.
The preparation method of the magnetic coupling hydroxyapatite nano particulate of embodiment 2, is carried out in accordance with the following steps：
1) under nitrogen protection atmosphere, by the FeCl of 1.7g3·6H2The FeCl of O and 0.60g2·4H2O is well mixed to be formed Mixture, then the mixture is dissolved in 200mL deionized waters, after mechanical agitation 30min, to being added dropwise over ammoniacal liquor in solution, Until the color blackening of solution, Magnetic Isolation is carried out after continuing mechanical agitation 3h, magnetisable material, then the Magnetic Materials to obtaining are obtained Matter deionized water and absolute ethyl alcohol cyclic washing, then dry 5h in 50 DEG C under vacuum, obtain 0.92g black Fe3O4Nano particle；
2) Fe of the 0.92g that will be prepared3O4The CaCl of nano particle, 0.89g2With the lauryl sodium sulfate of 1.15g It is well mixed to form mixture, then the mixture is dissolved in 120mL deionized waters, mechanical agitation 30min, then in the solution The Na for adding 40mL to contain 0.85g2CO3The aqueous solution, carry out Magnetic Isolation after continuing mechanical agitation 6h at room temperature, obtain magnetic Property material, then magnetisable material deionized water and absolute ethyl alcohol cyclic washing to obtaining, then under vacuum in 50 DEG C 5h is dried, the Fe of 1.2g is obtained3O4/CaCO3Nano particle presoma；
3) Fe of the 1.2g that will be prepared3O4/CaCO3It is 0.3mol/L's that nano particle presoma dissolves in 70mL concentration Na3PO4In the aqueous solution, uniform solution is obtained through sonic oscillation, solution is then transferred to 100mL autoclaves, 180 Under the conditions of DEG C after hydro-thermal reaction 3h, room temperature is cooled to, product is washed repeatedly, alcohol is washed, finally Magnetic Isolation again, vacuum is done The magnetic coupling hydroxyapatite nano particulate of embodiment 2 is obtained after dry, its form is Fe3O4Nano particle and hydroxy-apatite Spherical agglomeration thing or granule that stone nano particle uniformly distributes alternately, Fe3O4It is 5 with the mol ratio of hydroxyapatite:1.
Fig. 2 a are the Fe that embodiment 2 is prepared3O4The SEM figures of nano particle, its individual particle particle size is 20- 30nm；Fig. 2 b are the Fe that embodiment 2 is prepared3O4/CaCO3The SEM figures of nano particle presoma, from Fig. 2 b, small particle Fe3O4With block CaCO3Composition spherical agglomeration thing, wherein Fe3O4With CaCO3Uniformly distribute alternately, spherical agglomeration thing structure Stabilization；Fig. 2 c are the SEM figures of magnetic coupling hydroxyapatite nano particulate prepared by embodiment 2, from Fig. 2 c, with presoma Fe3O4/CaCO3Pattern slightly has difference, is substantially also the spherical agglomeration thing of monodispersity, and the spherical agglomeration thing is Fe3O4And hydroxyl Apatite is uniformly distributed the magnetic coupling hydroxyapatite nano particulate of composition.
The magnetic coupling hydroxyapatite nano particulate that embodiment 1 is prepared is used for Pb2+Removal, study its right Pb2+Fixed performance, experimental procedure is as follows：
1. 50mL Pb are prepared respectively in 5 conical flasks of 250mL2+Concentration is the solution of 400mg/L, uses HNO3With The NaOH aqueous solution adjusts the pH value of solution respectively so that the pH value of solution is respectively 2.0,3.0,4.0,5.0 and in 5 conical flasks 6.0, the magnetic coupling hydroxyapatite nano particulate for then preparing 50mg embodiments 1 is separately added into this 5 conical flasks In, conical flask is placed in Desk type constant-temperatureoscillator oscillator afterwards, temperature is set to 25 DEG C, and oscillation rate is 180r/min, and the time is 3h.
2. 3mL solution is taken respectively from above-mentioned 5 conical flasks with syringe, first filtered with the water system that aperture is 0.45 micron Head filters out magnetic coupling hydroxyapatite material, then by filtrate with Inductively coupled plasma optical emission spectrometer (ICP-AES) Measure, remaining metal ion content in solution after the solid lead reaction of acquisition.The magnetic hydroxylapatite is calculated to receive Rice grain is for Pb2+Saturated extent of adsorption reach 440mg/g.
The magnetic coupling hydroxyapatite nano particulate that embodiment 1 is prepared is at various ph values to Pb2+Stationarity Energy, the Ca to separating out2+Concentration and the Ca to being separated out in the aqueous solution containing lead ion2+The curve map of concentration is shown in Fig. 3, from absorption Calcium ion concentration change curve can be seen that magnetic coupling hydroxyapatite nano particulate in pH value=3-6, only in preceding solution There is micro Ca2+Separate out, show that the magnetic coupling hydroxyapatite nano particulate can be with stable existence；When pH value continues to be reduced to When 2, there is part Ca2+Separate out, show that the magnetic coupling hydroxyapatite nano particle fraction dissolves；But as treatment identical value pH Under when containing lead solution, as pH value=3-6, Ca2+Amount of precipitation increase (calcium ion concentration change curve in solution after absorption), Substantially and Pb simultaneously2+Fixed amount be consistent (adsorbed plumbum ion concentration curve), i.e. Pb2+In instead of hydroxyapatite Ca2+Position；There is substantial amounts of Ca when pH value continues to be reduced to 2, in mixed solution2+Separate out, and far above Pb2+Fixed amount, Mainly due to the dissolving of hydroxyapatite in strong acidic condition magnetic composite hydroxylapatite nanoparticle, and highly acid ring Border inhibits what the generation of lead deposits thing was caused.
The magnetic coupling hydroxyapatite nano particulate that embodiment 1 is prepared is used for Cd2+Removal, study its right Cd2+Fixed performance, experimental procedure is as follows：
1. 50mL Cd are prepared respectively in 1 conical flask of 250mL2+Concentration is the solution of 217mg/L, uses HNO3With The pH value that the NaOH aqueous solution adjusts solution respectively is 3.0, the magnetic coupling hydroxy-apatite for then preparing 50mg embodiments 1 In stone nanoparticle this conical flask, conical flask is placed in Desk type constant-temperatureoscillator oscillator afterwards, temperature is set to 25 DEG C, oscillation rate It is 180r/min, the time is 3h.
2. 3mL solution is distinguished from above-mentioned conical flask with syringe, first will with the water system filtering head that aperture is 0.45 micron Magnetic coupling hydroxyapatite material is filtered out, then filtrate is carried out with Inductively coupled plasma optical emission spectrometer (ICP-AES) Measurement, obtains solid Cd2+Remaining metal ion content in solution after reaction.It is calculated magnetic hydroxylapatite nanometer Grain is for Cd2+Saturated extent of adsorption reach 238mg/g.
The magnetic coupling hydroxyapatite nano particulate that embodiment 1 is prepared is used for Zn2+Removal, study its right Zn2+Fixed performance, experimental procedure is as follows：
1. 50mL Zn are prepared respectively in 1 conical flask of 250mL2+Concentration is the solution of 126mg/L, uses HNO3With The pH value that the NaOH aqueous solution adjusts solution respectively is 3.0, the magnetic coupling hydroxy-apatite for then preparing 50mg embodiments 1 In stone nanoparticle this conical flask, conical flask is placed in Desk type constant-temperatureoscillator oscillator afterwards, temperature is set to 25 DEG C, oscillation rate It is 180r/min, the time is 3h.
2. 3mL solution is distinguished from above-mentioned conical flask with syringe, first will with the water system filtering head that aperture is 0.45 micron Magnetic coupling hydroxyapatite material is filtered out, then filtrate is carried out with Inductively coupled plasma optical emission spectrometer (ICP-AES) Measurement, obtains solid Zn2+Remaining metal ion content in solution after reaction.It is calculated magnetic hydroxylapatite nanometer Grain is for Zn2+Saturated extent of adsorption reach 139mg/g.
The magnetic coupling hydroxyapatite nano particulate that embodiment 2 is prepared is used for Cu2+Removal, study its right Cu2+Fixed performance, experimental procedure is as follows：
1. 50mL Cu are prepared respectively in 1 conical flask of 250mL2+Concentration is the solution of 123mg/L, uses HNO3With The pH value that the NaOH aqueous solution adjusts solution respectively is 4.0, the magnetic coupling hydroxy-apatite for then preparing 50mg embodiments 1 In stone nanoparticle this conical flask, conical flask is placed in Desk type constant-temperatureoscillator oscillator afterwards, temperature is set to 25 DEG C, oscillation rate It is 180r/min, the time is 3h.
2. 3mL solution is distinguished from above-mentioned conical flask with syringe, first will with the water system filtering head that aperture is 0.45 micron Magnetic coupling hydroxyapatite material is filtered out, then filtrate is carried out with Inductively coupled plasma optical emission spectrometer (ICP-AES) Measurement, obtains solid Cu2+Remaining metal ion content in solution after reaction.It is calculated magnetic hydroxylapatite nanometer Grain is for Cu2+Saturated extent of adsorption reach 135mg/g.

Claims (4)

1. the preparation method of magnetic coupling hydroxyapatite nano particulate, it is characterised in that comprise the following steps：
1) under nitrogen protection atmosphere, by soluble trivalent iron salt with soluble divalent iron salt with (1.9-2.2):1 mol ratio It is well mixed to form mixture, then the mixture is dissolved in deionized water with the ratio of 0.5-0.7g/mL, mechanical agitation 10- After 30min, to ammoniacal liquor is added dropwise in solution, until the color blackening of solution, Magnetic Isolation is carried out after continuing mechanical agitation 0.5-1h, Magnetisable material, then magnetisable material deionized water and absolute ethyl alcohol cyclic washing to obtaining are obtained, then under vacuum 1-6h is dried in 45-80 DEG C, the particle size for obtaining black is the Fe of 20-30nm3O4Nano particle；
2) Fe that will be prepared3O4Nano particle, soluble calcium salt and lauryl sodium sulfate are according to 1:(1-10):1 mole Mixture is formed than well mixed, then the mixture is dissolved in deionized water with the ratio of 0.8-2.5g/mL, mechanical agitation 10-30min, then adds the Na with above-mentioned soluble calcium salt equimolar concentration in the solution2CO3, machinery is continued at room temperature and is stirred Magnetic Isolation is carried out after mixing 1-3h, magnetisable material is obtained, then to the magnetisable material deionized water and absolute ethyl alcohol that obtain repeatedly Washing, then dries 1-6h in 45-80 DEG C under vacuum, obtains Fe3O4/CaCO3Nano particle presoma；
3) Fe that will be prepared3O4/CaCO3Nano particle presoma dissolves in the Na that concentration is 0.15-0.3mol/L3PO4It is water-soluble In liquid, uniform solution is obtained through sonic oscillation, solution is then transferred to autoclave, the water under the conditions of 150-300 DEG C After thermal response 3-24h, room temperature is cooled to, product is washed repeatedly, alcohol is washed, finally Magnetic Isolation again, after vacuum drying i.e. Magnetic coupling hydroxyapatite nano particulate is obtained, its form is Fe3O4Nano particle and hydroxyapatite nanoparticle homogeneous phase Between be distributed spherical agglomeration thing, Fe3O4It is (1-10) with the mol ratio of hydroxyapatite:1.
2. the preparation method of magnetic coupling hydroxyapatite nano particulate according to claim 1, it is characterised in that step 1) the soluble trivalent iron salt described in is FeCl3、FeCl3·6H2O、Fe(NO3)3·9H2O and Fe2(SO4)3In one kind or Various, described soluble divalent iron salt is FeCl2、FeCl2·4H2O and FeSO4·7H2One or more in O.
3. the preparation method of magnetic coupling hydroxyapatite nano particulate according to claim 1 and 2, it is characterised in that step It is rapid 2) described in soluble calcium salt be CaCl2With Ca (NO3)2In one or two.
4. the magnetic coupling hydroxyapatite nano particulate that prepared by claim 1 is in treatment pH value in the heavy metal wastewater thereby of 2-3 Application.
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