CN104549127A - Magnetic composite hydroxyapatite nanoparticles as well as preparation method and application thereof - Google Patents
Magnetic composite hydroxyapatite nanoparticles as well as preparation method and application thereof Download PDFInfo
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- CN104549127A CN104549127A CN201510044086.2A CN201510044086A CN104549127A CN 104549127 A CN104549127 A CN 104549127A CN 201510044086 A CN201510044086 A CN 201510044086A CN 104549127 A CN104549127 A CN 104549127A
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Abstract
The invention discloses magnetic composite hydroxyapatite nanoparticles. The magnetic composite hydroxyapatite nanoparticles are composed of Fe3O4 nanoparticles and hydroxyapatite nanoparticles, wherein the molar ratio of the Fe3O4 to the hydroxyapatite is (1-10): 1; the magnetic composite hydroxyapatite nanoparticles are spherical aggregate or agglomerate in which the Fe3O4 nanoparticles and the hydroxyapatite nanoparticles are distributed evenly and alternately. The preparation method of the magnetic composite hydroxyapatite nanoparticles is simple; the nanoparticles are capable of efficiently removing heavy metal ions in sewage, and in the later treatment period, quick magnetic separation can be realized; the nanoparticles have the adsorbing capacity of 440mg/g to lead ions, the adsorbing capacity of 238mg/g to cadmium ions, the adsorbing capacity of 139mg/g to zinc ions and the adsorbing capacity of 135mg/g to copper ions in the sewage; the magnetic composite hydroxyapatite nanoparticles have a rapid magnetic response characteristic, and are capable of realizing rapid solid-liquid separation with an external magnetic field, and the separation process is high in separation efficiency, and simple and efficient to operate; and besides, the nanoparticles are not residual in water and do not cause secondary pollution to the water and the environment.
Description
Technical field
The present invention relates to technical field of material, be specifically related to a kind of magnetic coupling hydroxyapatite nano particulate and its preparation method and application.
Background technology
The development of modern economy and industrially need the extensive development that have stimulated large quantities of highly energy-consumings such as battery manufacturing industry, metal smelt, mining, high pollution enterprise, containing a large amount of heavy metal ion in the waste water that these enterprises produce, the waste water that poisonous ion discharges with enterprise flows into river, river, go deep into underground water, heavy damage ecological environment.Therefore solve heavy metal pollution problem, the ecological environment of protection human survival has become the problem that countries in the world need solution badly.
Hydroxyapatite is a kind of material common in current Industrial Waste Water Treatments, for the removal of heavy metal in sewage.Native hydroxyl apatite is cheap and easy to get, has certain wastewater treatment efficiency, such as, can reach 28.6mg/g to the adsorbance of lead ion; Prof. Du Yucang compared with pure, that specific area is large, nano level hydroxyapatite can significantly improve heavy metal ions in sewage removal capacity, pattern depending on synthetic product is different, be 260-416mg/g to the adsorbance of lead ion, but hydroxyapatite is generally with Powdered existence, there is the defects such as Separation of Solid and Liquid difficulty, the rate of settling be low in the Industrial Waste Water Treatments later stage, can increase the cost of commercial Application to a certain extent, hydroxyapatite residual in water body after using has certain toxic and side effect to microorganisms in water.
Magnetic separation technique starts to be applied to engineering of water treatment as an emerging technology at present, magnetic separation technique is the effect by magnetic field force, a kind of physical separation method that the material different to magnetic is separated, in the process heavy metal ion later stage, externally-applied magnetic field can be separated fast from the aqueous solution, thus overcome the defect that adsorbent reclaims difficulty, avoid nano adsorber to the toxic and side effect of microorganism and human body.About magnetic Nano material to be combined with hydroxyapatite report less, as CN 103541005A discloses a kind of preparation method of magnetic hydroxylapatite crystal whisker ball, the method is with soluble calcium salt, solubility microcosmic salt, the double-deck nano ferriferrous oxide ferrofluid modified is raw material, urea is acidity-basicity regulator, magnetic hydroxylapatite crystal whisker ball is prepared under water bath condition, can be used for target medicine carrier, the fields such as biological engineering material, but the nano ferriferrous oxide used in the method experimentation needs to modify through double-deck, this adds the complexity of method to a certain extent, and for modifying the coating material generally more difficult removal added by tri-iron tetroxide, this too increases the complexity of production to a certain extent.H.Yang, S.Masse, H.Zhang, C.H é lary, L.Li, T.Coradin, Surface reactivity of hydroxyapatite nanocoatings depositedon iron oxide magnetic spheres toward toxic metals, J.Colloid Inter.Sci.417 (2014)
1-8. report fe 3 o 4 @Hydroxyapatitecomplex microsphere for the removal of lead ion, need in this composite particles building-up process to use aspartic acid process to carry out surface modification, 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 extractedfrom eggshell waste.J.Hazard.Mater.2010,177 (1-3), the Li Dengxiao of 126-130. report utilizes discarded egg shell to synthesize the removal of magnetic calcium hydroxy phosphate composite for lead ion, but the removal effect of this material scatter difference to lead ion is limited.CN102500333A proposes with natural zeolite, hydroxyapatite, tri-iron tetroxide, shitosan and cationic surfactant prepare a kind of magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition as stock, can be used as magnetic organic/inorganic composite material adsorbent, and this adsorbent is applied to humic acid in removal water, Congo red heavy metal contaminants such as grade organic pollution and copper ion etc., but raw material complexity prepared by this material, requirement is had to the pH value of the sewage of process, the pH value of sewage is needed to be adjusted to partial neutral (6.0-7.0) before treatment, operability is poor, and absorption property is not high, and (humic acid and Congo red adsorbance are at 80mg/kg, cupric ion adsorption is at 27mg/kg), this limits its application in sewage disposal to a certain extent.
Summary of the invention
Technical problem to be solved by this invention is: for the deficiencies in the prior art, provides a kind of magnetic coupling hydroxyapatite nano particulate, and its preparation method is simple, be easy to operation, can be applicable to process heavy metal wastewater thereby; This nanoparticle has excellent acid resistance, almost Iron pick up is not had in pH=1.0-3.0 situation yet, this nanoparticle is applicable to the heavy metal wastewater thereby processing various pH value, efficiently can remove heavy metal ions in sewage and process the later stage can realize rapid magnetic be separated.
The present invention solves the problems of the technologies described above adopted technical scheme: magnetic coupling hydroxyapatite nano particulate, by Fe
3o
4nano particle and hydroxyapatite nanoparticle form, Fe
3o
4be (1-10) with the mol ratio of hydroxyapatite: 1, this magnetic coupling hydroxyapatite nano particulate is Fe
3o
4the spherical agglomeration thing that nano particle and hydroxyapatite nanoparticle evenly distribute alternately or granule.
The preparation method of magnetic coupling hydroxyapatite nano particulate, comprises the following steps:
1) under nitrogen protection atmosphere; by solubility trivalent iron salt and solubility divalent iron salt with (1.9-2.2): the mixed in molar ratio of 1 evenly forms mixture; again this mixture is dissolved in deionized water with the ratio of 0.5-0.7g/mL; after mechanical agitation 10-30min; ammoniacal liquor is dripped in solution; until the color blackening of solution; Magnetic Isolation is carried out after continuing mechanical agitation 0.5-1h; obtain magnetisable material; again to the magnetisable material deionized water obtained and absolute ethyl alcohol cyclic washing; then under vacuum in 45-80 DEG C of dry 1-6h, the Fe of black is obtained
3o
4nano particle;
2) Fe will prepared
3o
4nano particle, soluble calcium salt and lauryl sodium sulfate are according to 1:(1-10): the mixed in molar ratio of 1 evenly forms mixture, again this mixture is dissolved in deionized water with the ratio of 0.8-2.5g/mL, mechanical agitation 10-30min, adds the Na with molar concentrations such as above-mentioned soluble calcium salts subsequently in the solution
2cO
3, carry out Magnetic Isolation after at room temperature continuing mechanical agitation 1-3h, obtain magnetisable material, then to the magnetisable material deionized water obtained and absolute ethyl alcohol cyclic washing, then under vacuum in 45-80 DEG C of dry 1-6h, obtain Fe
3o
4/ CaCO
3nano particle presoma;
3) Fe will prepared
3o
4/ CaCO
3nano particle presoma dissolves in the Na that concentration is 0.15-0.3mol/L
3pO
4in the aqueous solution, uniform solution is obtained through sonic oscillation, then solution is transferred to autoclave, after 150-300 DEG C of Water Under thermal response 3-24h, be cooled to room temperature, product washed repeatedly, alcohol wash, finally Magnetic Isolation again, namely obtain magnetic coupling hydroxyapatite nano particulate after vacuum drying, its form is Fe
3o
4the spherical agglomeration thing that nano particle and hydroxyapatite nanoparticle evenly distribute alternately or granule, Fe
3o
4be (1-10) with the mol ratio of hydroxyapatite: 1.
Lauryl sodium sulfate (being called for short SDS) is a kind of surfactant, as a kind of anion surfactant, there is certain critical micelle concentration, when exceeding the critical micelle concentration of this surfactant, this anion surfactant is easily agglomerated into microballoon micelle, due to the interaction between surfactant and calcium ion, this microballoon micelle plays and impels calcium carbonate granule nucleation in the Crystallization of calcium carbonate, grow and be agglomerated into the effect of large particle, under mechanical agitation, ferroferric oxide nano granules can evenly embed in the space between calcium carbonate granule in addition.
As preferably, step 1) described in solubility trivalent iron salt be FeCl
3, FeCl
36H
2o, Fe (NO
3)
39H
2o and Fe
2(SO
4)
3in one or more, described solubility divalent iron salt is FeCl
2, FeCl
24H
2o and FeSO
47H
2one or more in O.
As preferably, step 2) described in soluble calcium salt be CaCl
2with Ca (NO
3)
2in one or both.
The application of magnetic coupling hydroxyapatite nano particulate of the present invention in process heavy metal wastewater thereby.Magnetic coupling hydroxyapatite nano particulate of the present invention has excellent acid resistance, does not also almost have Iron pick up, efficiently can remove the Pb in sewage in pH value=1.0-3.0 situation
2+, Cd
2+, Zn
2+, Cu
2+etc. heavy metal ion and the process later stage can realize rapid magnetic is separated, adopt permanent magnet can in short time (as in 1 minute) effectively Magnetic Isolation, separative efficiency can reach more than 98%, noresidue in water body.For the sewage of the different pH value containing heavy metal ion, the adsorption mechanism of magnetic coupling hydroxyapatite nano particulate heavy metal ion of the present invention is different.With magnetic coupling hydroxyapatite nano particulate of the present invention to Pb
2+be adsorbed as example, during pH value=3-6, based on ion-exchange with absorption complex mechanism, its reaction equation is:
Ca
10(PO
4)
6(OH)
2+xPb
2+→xCa
2++Ca
10-xPb
x(PO
4)
6(OH)
2
As pH value=1-3, be mainly dissolving-PRECIPITATION MECHANISM, the reaction equation of course of dissolution is:
nCa
10(PO
4)
6(OH)
2+4mH
+→10nCa
2++3mHPO
4 2-+(2n-m)(PO
4)
3(OH)
10-+mH
2O
The reaction equation of precipitation process is:
(x+5y)Pb
2++xHPO
4 2-+y(PO
4)
3(OH)
10-→xPbHPO
4+yPb
5(PO
4)
3(OH)
No matter be which kind of adsorption mechanism, all have higher adsorbance to heavy metal ions in sewage, the complexes or precipitates that absorption is formed, the phase is all by Magnetic Isolation and Fe after treatment
3o
4be separated quickly and easily from water body together, separative efficiency is high, noresidue in water body, can not to water body and environment.Therefore, when magnetic coupling hydroxyapatite nano particulate of the present invention is applied to waste water control, not by the restriction of pH value of sewage water, without the need to regulating the pH value of sewage in advance before process, applied widely, be applicable to the heavy metal wastewater thereby of various pH value.
Compared with prior art, the invention has the advantages that: the inventive method is at Fe
3o
4/ CaCO
3do not make the organic solvent such as spent glycol, isopropyl alcohol in the preparation process of nano particle presoma, because organic solvent can increase cost, and organic solvent has certain toxicity; The Fe of synthesis
3o
4nano particle does not in use need to modify its surface, Fe
3o
4get final product and CaCO under as the lauryl sodium sulfate effect of surfactant
3form the spherical agglomeration thing or granule shape Fe that evenly distribute alternately
3o
4/ CaCO
3nano particle presoma, this Fe
3o
4/ CaCO
3nano particle presoma uses hydrothermal method can prepare magnetic coupling hydroxyapatite nano particulate, and preparation method is simple; Magnetic coupling hydroxyapatite nano particulate of the present invention is Fe
3o
4the spherical agglomeration thing that nano particle and hydroxyapatite nanoparticle evenly distribute alternately or granule shape monodispersity particle, have excellent acid resistance, in pH value=1.0-3.0 situation, also almost do not have Iron pick up; Magnetic coupling hydroxyapatite nano particulate of the present invention is applicable to the heavy metal wastewater thereby processing various pH value, efficiently can remove heavy metal ions in sewage and process the later stage can realize rapid magnetic be separated, 440mg/g can be reached to the adsorbance of lead ion in sewage, the adsorbance of cadmium ion can reach 238mg/g, the adsorbance of zinc ion can reach 139mg/g, and the adsorbance of copper ion can reach 135mg/g; Be compared to nonmagnetic simple hydroxyapatite, magnetic coupling hydroxyapatite nano particulate of the present invention has quick magnetic response characteristic, externally-applied magnetic field just can realize quick Separation of Solid and Liquid, separative efficiency is high, simple to operate, efficient, noresidue in water body, can not cause secondary pollution to water body and environment.
Accompanying drawing explanation
Fig. 1 is Fe prepared by embodiment 1
3o
4nano particle (#2), Fe
3o
4/ CaCO
3the XRD comparison diagram of nano particle presoma (#1) and magnetic coupling hydroxyapatite nano particulate (#3);
Fig. 2 a is Fe prepared by embodiment 2
3o
4the SEM figure of nano particle;
Fig. 2 b is Fe prepared by embodiment 2
3o
4/ CaCO
3the SEM figure of nano particle presoma;
Fig. 2 c is the SEM figure of magnetic coupling hydroxyapatite nano particulate prepared by embodiment 2;
Fig. 3 is that the magnetic coupling hydroxyapatite nano particulate for preparing of embodiment 1 is at various ph values to Pb
2+fixed performance, to separate out Ca
2+concentration and to containing the Ca separated out in the aqueous solution of lead ion
2+the curve map of concentration.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
The preparation method of the magnetic coupling hydroxyapatite nano particulate of embodiment 1, carries out in accordance with the following steps:
1) under nitrogen protection atmosphere, by the FeCl of 0.85g
36H
2the FeCl of O and 0.30g
24H
2o mixes formation mixture, again this mixture is dissolved in 200mL deionized water, after mechanical agitation 30min, in solution, dropwise add ammoniacal liquor, until the color blackening of solution, after continuing mechanical agitation 1h, carry out Magnetic Isolation, obtain magnetisable material, again to the magnetisable material deionized water obtained and absolute ethyl alcohol cyclic washing, then under vacuum in 45 DEG C of dry 6h, obtain the Fe of 0.46g black
3o
4nano particle;
2) Fe of 0.46g will prepared
3o
4the CaCl of nano particle, 0.89g
2mix formation mixture with the lauryl sodium sulfate of 1.15g, then this mixture is dissolved in 120mL deionized water, mechanical agitation 30min, add the Na that 40mL contains 0.85g subsequently in the solution
2cO
3the aqueous solution, at room temperature continue to carry out Magnetic Isolation after mechanical agitation 3h, obtain magnetisable material, then to the magnetisable material deionized water obtained and absolute ethyl alcohol cyclic washing, then under vacuum in 45 DEG C of dry 6h, obtain the Fe of 0.75g
3o
4/ CaCO
3nano particle presoma;
3) Fe of 0.75g will prepared
3o
4/ CaCO
3nano particle presoma dissolves in the Na that 70mL concentration is 0.15mol/L
3pO
4in the aqueous solution, uniform solution is obtained through sonic oscillation, then solution is transferred to 100mL autoclave, after 180 DEG C of Water Under thermal response 3h, be cooled to room temperature, product washed repeatedly, alcohol wash, finally Magnetic Isolation again, namely obtain the magnetic coupling hydroxyapatite nano particulate of embodiment 1 after vacuum drying, its form is Fe
3o
4the spherical agglomeration thing that nano particle and hydroxyapatite nanoparticle evenly distribute alternately or granule, Fe
3o
4be 5:2 with the mol ratio of hydroxyapatite.
Fig. 1 is the Fe that embodiment 1 prepares
3o
4nano particle (#2), Fe
3o
4/ CaCO
3the XRD comparison diagram of nano particle presoma (#1) and magnetic coupling hydroxyapatite nano particulate (#3), existingly in magnetic coupling hydroxyapatite nano particulate as can be seen from Figure 1 belongs to Fe
3o
4phase: (220), (311), (400), (511), (440), also the phase belonging to hydroxyapatite is had: (002), (211), (300), (202), (130), (222), (213), and Fe
3o
4/ CaCO
3nano particle presoma has changed into magnetic coupling hydroxyapatite nano particulate completely after hydro-thermal reaction.
The preparation method of the magnetic coupling hydroxyapatite nano particulate of embodiment 2, carries out in accordance with the following steps:
1) under nitrogen protection atmosphere, by the FeCl of 1.7g
36H
2the FeCl of O and 0.60g
24H
2o mixes formation mixture, again this mixture is dissolved in 200mL deionized water, after mechanical agitation 30min, in solution, dropwise add ammoniacal liquor, until the color blackening of solution, after continuing mechanical agitation 3h, carry out Magnetic Isolation, obtain magnetisable material, again to the magnetisable material deionized water obtained and absolute ethyl alcohol cyclic washing, then under vacuum in 50 DEG C of dry 5h, obtain the Fe of 0.92g black
3o
4nano particle;
2) Fe of 0.92g will prepared
3o
4the CaCl of nano particle, 0.89g
2mix formation mixture with the lauryl sodium sulfate of 1.15g, then this mixture is dissolved in 120mL deionized water, mechanical agitation 30min, add the Na that 40mL contains 0.85g subsequently in the solution
2cO
3the aqueous solution, at room temperature continue to carry out Magnetic Isolation after mechanical agitation 6h, obtain magnetisable material, then to the magnetisable material deionized water obtained and absolute ethyl alcohol cyclic washing, then under vacuum in 50 DEG C of dry 5h, obtain the Fe of 1.2g
3o
4/ CaCO
3nano particle presoma;
3) Fe of 1.2g will prepared
3o
4/ CaCO
3nano particle presoma dissolves in the Na that 70mL concentration is 0.3mol/L
3pO
4in the aqueous solution, uniform solution is obtained through sonic oscillation, then solution is transferred to 100mL autoclave, after 180 DEG C of Water Under thermal response 3h, be cooled to room temperature, product washed repeatedly, alcohol wash, finally Magnetic Isolation again, namely obtain the magnetic coupling hydroxyapatite nano particulate of embodiment 2 after vacuum drying, its form is Fe
3o
4the spherical agglomeration thing that nano particle and hydroxyapatite nanoparticle evenly distribute alternately or granule, Fe
3o
4be 5:1 with the mol ratio of hydroxyapatite.
Fig. 2 a is the Fe that embodiment 2 prepares
3o
4the SEM figure of nano particle, its individual particle particle size is 20-30nm; Fig. 2 b is the Fe that embodiment 2 prepares
3o
4/ CaCO
3the SEM figure of nano particle presoma, from Fig. 2 b, the Fe of small particle diameter
3o
4with the CaCO of bulk
3composition spherical agglomeration thing, wherein Fe
3o
4with CaCO
3evenly distribute alternately, spherical agglomeration thing Stability Analysis of Structures; Fig. 2 c is the SEM figure of magnetic coupling hydroxyapatite nano particulate prepared by embodiment 2, from Fig. 2 c, with presoma Fe
3o
4/ CaCO
3pattern is difference slightly, and be also the spherical agglomeration thing of monodispersity substantially, this spherical agglomeration thing is Fe
3o
4the magnetic coupling hydroxyapatite nano particulate of composition is uniformly distributed with hydroxyapatite.
Magnetic coupling hydroxyapatite nano particulate embodiment 1 prepared is used for Pb
2+removal, study it to Pb
2+fixed performance, experimental procedure is as follows:
1. in the conical flask of 5 250mL, 50mL Pb is prepared respectively
2+concentration is the solution of 400mg/L, uses HNO
3the pH value of solution is adjusted respectively with the NaOH aqueous solution, the pH value of solution in 5 conical flasks is made to be respectively 2.0,3.0,4.0,5.0 and 6.0, then magnetic coupling hydroxyapatite nano particulate 50mg embodiment 1 prepared adds in these 5 conical flasks respectively, afterwards conical flask is placed in Desk type constant-temperatureoscillator oscillator, temperature is set to 25 DEG C, oscillation rate is 180r/min, and the time is 3h.
2. from above-mentioned 5 conical flasks, 3mL solution is got with syringe respectively, first with the water system filtering head that aperture is 0.45 micron, magnetic coupling hydroxyapatite material is filtered out, again filtrate is measured with Inductively coupled plasma optical emission spectrometer (ICP-AES), remaining metal ion content in solution after obtaining solid plumbous reaction.Calculate this magnetic hydroxylapatite nano particle for Pb
2+saturated extent of adsorption reach 440mg/g.
The magnetic coupling hydroxyapatite nano particulate that embodiment 1 prepares is at various ph values to Pb
2+fixed performance, to separate out Ca
2+concentration and to containing the Ca separated out in the aqueous solution of lead ion
2+the curve map of concentration is shown in Fig. 3, and before absorption, solution, calcium ion concentration change curve can find out that magnetic coupling hydroxyapatite nano particulate is when pH value=3-6, only has the Ca of trace
2+separate out, show that this magnetic coupling hydroxyapatite nano particulate can stable existence; When pH value continues to be reduced to 2, there is part Ca
2+separate out, show that this magnetic coupling hydroxyapatite nano particle fraction dissolves; But when process identical value pH under containing lead solution time, as pH value=3-6, Ca
2+amount of precipitation increase (absorption after solution in calcium ion concentration change curve), basic and Pb simultaneously
2+fixed amount be consistent (by adsorpting lead ion concentration curve), i.e. Pb
2+instead of Ca in hydroxyapatite
2+position; When pH value continues to be reduced to 2, in mixed solution, there is a large amount of Ca
2+separate out, and far above Pb
2+fixed amount, mainly due to the dissolving of hydroxyapatite in strong acidic condition magnetic composite hydroxylapatite nanoparticle, and strong acidic environment inhibits the generation of lead deposits thing to cause.
Magnetic coupling hydroxyapatite nano particulate embodiment 1 prepared is used for Cd
2+removal, study it to Cd
2+fixed performance, experimental procedure is as follows:
1. in the conical flask of 1 250mL, 50mL Cd is prepared respectively
2+concentration is the solution of 217mg/L, uses HNO
3the pH value adjusting solution with the NaOH aqueous solution is respectively 3.0, then, in this conical flask of magnetic coupling hydroxyapatite nano particulate 50mg embodiment 1 prepared, be placed in Desk type constant-temperatureoscillator oscillator by conical flask afterwards, temperature is set to 25 DEG C, oscillation rate is 180r/min, and the time is 3h.
2. with syringe difference 3mL solution from above-mentioned conical flask, first with the water system filtering head that aperture is 0.45 micron, magnetic coupling hydroxyapatite material is filtered out, again filtrate is measured with Inductively coupled plasma optical emission spectrometer (ICP-AES), obtain solid Cd
2+remaining metal ion content in solution after reaction.Calculate this magnetic hydroxylapatite nano particle for Cd
2+saturated extent of adsorption reach 238mg/g.
Magnetic coupling hydroxyapatite nano particulate embodiment 1 prepared is used for Zn
2+removal, study it to Zn
2+fixed performance, experimental procedure is as follows:
1. in the conical flask of 1 250mL, 50mL Zn is prepared respectively
2+concentration is the solution of 126mg/L, uses HNO
3the pH value adjusting solution with the NaOH aqueous solution is respectively 3.0, then, in this conical flask of magnetic coupling hydroxyapatite nano particulate 50mg embodiment 1 prepared, be placed in Desk type constant-temperatureoscillator oscillator by conical flask afterwards, temperature is set to 25 DEG C, oscillation rate is 180r/min, and the time is 3h.
2. with syringe difference 3mL solution from above-mentioned conical flask, first with the water system filtering head that aperture is 0.45 micron, magnetic coupling hydroxyapatite material is filtered out, again filtrate is measured with Inductively coupled plasma optical emission spectrometer (ICP-AES), obtain solid Zn
2+remaining metal ion content in solution after reaction.Calculate this magnetic hydroxylapatite nano particle for Zn
2+saturated extent of adsorption reach 139mg/g.
Magnetic coupling hydroxyapatite nano particulate embodiment 2 prepared is used for Cu
2+removal, study it to Cu
2+fixed performance, experimental procedure is as follows:
1. in the conical flask of 1 250mL, 50mL Cu is prepared respectively
2+concentration is the solution of 123mg/L, uses HNO
3the pH value adjusting solution with the NaOH aqueous solution is respectively 4.0, then, in this conical flask of magnetic coupling hydroxyapatite nano particulate 50mg embodiment 1 prepared, be placed in Desk type constant-temperatureoscillator oscillator by conical flask afterwards, temperature is set to 25 DEG C, oscillation rate is 180r/min, and the time is 3h.
2. with syringe difference 3mL solution from above-mentioned conical flask, first with the water system filtering head that aperture is 0.45 micron, magnetic coupling hydroxyapatite material is filtered out, again filtrate is measured with Inductively coupled plasma optical emission spectrometer (ICP-AES), obtain solid Cu
2+remaining metal ion content in solution after reaction.Calculate this magnetic hydroxylapatite nano particle for Cu
2+saturated extent of adsorption reach 135mg/g.
Claims (5)
1. magnetic coupling hydroxyapatite nano particulate, is characterized in that by Fe
3o
4nano particle and hydroxyapatite nanoparticle form, Fe
3o
4be (1-10) with the mol ratio of hydroxyapatite: 1, this magnetic coupling hydroxyapatite nano particulate is Fe
3o
4the spherical agglomeration thing that nano particle and hydroxyapatite nanoparticle evenly distribute alternately or granule.
2. the preparation method of magnetic coupling hydroxyapatite nano particulate, is characterized in that comprising the following steps:
1) under nitrogen protection atmosphere; by solubility trivalent iron salt and solubility divalent iron salt with (1.9-2.2): the mixed in molar ratio of 1 evenly forms mixture; again this mixture is dissolved in deionized water with the ratio of 0.5-0.7g/mL; after mechanical agitation 10-30min; ammoniacal liquor is dripped in solution; until the color blackening of solution; Magnetic Isolation is carried out after continuing mechanical agitation 0.5-1h; obtain magnetisable material; again to the magnetisable material deionized water obtained and absolute ethyl alcohol cyclic washing; then under vacuum in 45-80 DEG C of dry 1-6h, the Fe of black is obtained
3o
4nano particle;
2) Fe will prepared
3o
4nano particle, soluble calcium salt and lauryl sodium sulfate are according to 1:(1-10): the mixed in molar ratio of 1 evenly forms mixture, again this mixture is dissolved in deionized water with the ratio of 0.8-2.5g/mL, mechanical agitation 10-30min, adds the Na with molar concentrations such as above-mentioned soluble calcium salts subsequently in the solution
2cO
3, carry out Magnetic Isolation after at room temperature continuing mechanical agitation 1-3h, obtain magnetisable material, then to the magnetisable material deionized water obtained and absolute ethyl alcohol cyclic washing, then under vacuum in 45-80 DEG C of dry 1-6h, obtain Fe
3o
4/ CaCO
3nano particle presoma;
3) Fe will prepared
3o
4/ CaCO
3nano particle presoma dissolves in the Na that concentration is 0.15-0.3mol/L
3pO
4in the aqueous solution, uniform solution is obtained through sonic oscillation, then solution is transferred to autoclave, after 150-300 DEG C of Water Under thermal response 3-24h, be cooled to room temperature, product washed repeatedly, alcohol wash, finally Magnetic Isolation again, namely obtain magnetic coupling hydroxyapatite nano particulate after vacuum drying, its form is Fe
3o
4the spherical agglomeration thing that nano particle and hydroxyapatite nanoparticle evenly distribute alternately or granule, Fe
3o
4be (1-10) with the mol ratio of hydroxyapatite: 1.
3. the preparation method of magnetic coupling hydroxyapatite nano particulate according to claim 2, is characterized in that step 1) described in solubility trivalent iron salt be FeCl
3, FeCl
36H
2o, Fe (NO
3)
39H
2o and Fe
2(SO
4)
3in one or more, described solubility divalent iron salt is FeCl
2, FeCl
24H
2o and FeSO
47H
2one or more in O.
4. the preparation method of the magnetic coupling hydroxyapatite nano particulate according to Claims 2 or 3, is characterized in that step 2) described in soluble calcium salt be CaCl
2with Ca (NO
3)
2in one or both.
5. the application of magnetic coupling hydroxyapatite nano particulate according to claim 1 in process heavy metal wastewater thereby.
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