CN102327768B - Imido magnetic nano-adsorbent as well as preparation method and application thereof - Google Patents
Imido magnetic nano-adsorbent as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an imido magnetic nano-adsorbent. The adsorbent is formed by covalent cross linkage of magnetic nanoparticles and polyethyleneimine, wherein the magnetic nanoparticles mainly consists of nano ferroferric oxide, and a layer of gamma-Fe2O3 particles is coated on the surface of the magnetic nanoparticles. The invention correspondingly discloses a preparation method of the adsorbent. The preparation method comprises the following steps: preparation of the magnetic nanoparticles and covalent cross linkage. The invention further correspondingly discloses an application of the adsorbent in treating heavy metal wastewater. The magnetic nano-adsorbent has the advantage of stable magnetic property in the presence of strong acid and strong alkali, and can be easily and rapidly separated from a liquid phase, thus being suitable for various operating environments; and in addition, the adsorbent can be regenerated by simple acid or alkali treatment. The preparation method of the adsorbent has the advantages of simple process and low cost; and the adsorbent can be used for realizing selective adsorption (up to almost 100%) on zinc and lead in application to treatment of the heavy metal wastewater.
Description
Technical field
The present invention relates to heavy metal containing wastewater treatment field, relate in particular to a kind of magnetic nanometer adsorbent and preparation method thereof and the application of this adsorbent in processing heavy metal wastewater thereby of imido grpup.
Background technology
Heavy metal pollution of water body has caused serious harm to publilc health and ecological environment.Industrial wastewater is the main source of heavy metal pollution, conventionally in waste water, has comprised multiple harmful heavy metal.Such as, then in ore dressing industry, plumbous and zinc almost exists simultaneously, thereby they have similar geochemical behaviour.In industries such as chemical industry, plating, fuel makings, also may produce the waste water that simultaneously contains lead and zinc in addition.From healthy and economic angle, optionally remove, recovery and reuse heavy metal species is very important.
As one of method of repairing heavy metal pollution, absorption method is easy to operate with it, the kind of adsorbent is various, flexible design, easily regeneration and the waste water processed are suitable for the advantages such as reuse and become one and be widely used and processing method efficiently.At present, a certain heavy metal of selective absorption has caused and has studied widely interest.The synthetic of metal polymer based on molecular imprinting can optionally be adsorbed specific heavy metal.Amido, imido grpup and mercapto-functionalized mesoporous adsorbent also can carry out by the specific binding with a certain metal optionally Adsorption of Heavy Metals.
Although research and application aspect at selective absorption heavy metal have obtained certain effect, but it is also not nearly enough perfect to have the adsorbent of selectivity and the synthetic method of adsorbent, and the adsorption rate of adsorbent is not high, and recycling rate of waterused is low, select the heavy metal of absorption to reclaim difficulty, and complicated operation.
Summary of the invention
Technical problem to be solved by this invention is: for the deficiencies in the prior art, the magnetic nanometer adsorbent of the imido grpup that a kind of high adsorption rate, stable chemical nature is provided and can reuses, and the corresponding preparation method that a kind of this adsorbent is provided, and also correspondingly provide the application of a kind of this adsorbent in processing heavy metal wastewater thereby.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A magnetic nanometer adsorbent for imido grpup, described adsorbent is formed by magnetic nano-particle and polymine covalent cross-linking, and described magnetic nano-particle is mainly comprised of nano ferriferrous oxide, and the surface of described magnetic nano-particle is coated with one deck γ – Fe
2o
3particle.In described adsorbent, preferably, the particle diameter of described magnetic nanometer adsorbent is about 60nm.
As a total inventive concept, the present invention is the corresponding preparation method that a kind of above-mentioned magnetic nanometer adsorbent is provided also, comprises the following steps:
(1) prepare magnetic nano-particle: first synthesis of nano tri-iron tetroxide, then tri-iron tetroxide is calcined to 60min~80min at 300 ℃~350 ℃, obtain surface and be coated with one deck γ – Fe
2o
3the magnetic nano-particle of particle (generates γ – Fe in calcination processing
2o
3there is magnetic, but its acid-resisting and antioxygenic property are better than tri-iron tetroxide, can stop the further oxidation of tri-iron tetroxide, improved the chemical stability of nano material); Synthetic tri-iron tetroxide preferably and ferric trichloride mixed solution ferrous by dichloride makes with ammoniacal liquor reaction;
(2) covalent cross-linking: described magnetic nano-particle is joined in sodium laurate solution and activated, through cleaning separation, then transfer in polyethyleneimine: amine aqueous solution and carry out mechanical agitation reaction, obtain the magnetic nanometer adsorbent of imido grpup after having reacted; Preferably, the concentration of sodium laurate solution is 1mol/L~2mol/L, and pH value is 9~11, and soak time is 120min~150min, and activation temperature is 60 ℃~80 ℃; The volumetric concentration of polyethyleneimine: amine aqueous solution is preferably 5%~8%, can utilize volumetric concentration is 50% methyl alcohol or dissolve with ethanol solution polymine, thereby obtain volumetric concentration and be 5%~8% polyethyleneimine: amine aqueous solution, mechanical agitation reaction temperature is preferably 60 ℃~80 ℃, and the mechanical agitation reaction time is preferably 90min~120min.
As a total inventive concept, the present invention also provides the application in Adsorption of Heavy Metals of magnetic nanometer adsorbent that above-mentioned magnetic nanometer adsorbent or above-mentioned preparation method make.
The magnetic nanometer adsorbent that a kind of above-mentioned magnetic nanometer adsorbent or above-mentioned preparation method make adsorbs zinc and plumbous application in plumbous zinc binary metal solution simultaneously, comprise the following steps: in plumbous zinc binary metal solution, add disodium ethylene diamine tetraacetate (EDTA), the molar concentration rate that makes EDTA in mixed solution and plumbous zinc metal ion is (0~0.5): 1, the pH value that regulates again mixed solution is 6~7, then add described adsorbent, make its concentration in mixed solution be controlled at 0.8g/L~2g/L, reaction 240min~300min, completes absorption.
The magnetic nanometer adsorbent that a kind of above-mentioned magnetic nanometer adsorbent or above-mentioned preparation method make is selected the application of absorption zinc in plumbous zinc binary metal solution, comprise the following steps: in plumbous zinc binary metal solution, add EDTA, the molar concentration rate that makes EDTA in mixed solution and plumbous zinc metal ion is (0.6~1.0): 1, the pH value that regulates again mixed solution is 5.5~7, then add described adsorbent, make its concentration in mixed solution be controlled at 0.8g/L~2g/L, reaction 240min~300min, completes absorption.In this absorption system, the existence form of zinc more than 90% is Zn
2+, and lead is mainly with PbEDTA
2-form exist.
In above-mentioned application, further, to above-mentioned completing, rear absorption of absorption there are the adsorbent of zinc and zinc to recycle, comprise the following steps: (selective absorption zinc meets typical Cation adsorption type to have the adsorbent of zinc to join the hydrochloric acid solution that concentration is 0.04mol/L~0.07mol/L absorption, along with the rising of pH value of solution, adsorption capacity increases, therefore select hydrochloric acid as actified solution) middle wash-out, the consumption of the adsorbent that described absorption has zinc in every liter of hydrochloric acid solution is 1g~1.5g, then at room temperature shake 60min~90min, Magnetic Isolation goes out adsorbent, through cleaning to neutrality, obtain the adsorbent of regeneration, repeatedly for adsorbing the wash-out of the adsorbent that has zinc, until elution efficiency is less than 90%, make zinc obtain enrichment the hydrochloric acid solution containing zinc obtaining after wash-out first.
In above-mentioned application, further, utilize the adsorbent of regeneration obtained above to adsorb the lead of (zinc is selectively adsorbed) in above-mentioned plumbous zinc binary metal solution, comprise the following steps: the pH value of the plumbous zinc binary metal solution that adjusting zinc has selectively been adsorbed is 1.5~3.5, then the adsorbent that adds described regeneration, make its concentration in mixed solution be controlled at 0.8g/L~2g/L, reaction 240min~300min, completes absorption.
The magnetic nanometer adsorbent that a kind of above-mentioned magnetic nanometer adsorbent or above-mentioned preparation method make is selected the application of Adsorption of Lead in plumbous zinc binary metal solution, comprise the following steps: in plumbous zinc binary metal solution, add EDTA, making EDTA in mixed solution and the molar concentration rate of plumbous zinc metal ion is 0.7: 1, the pH value that regulates again mixed solution is 1.5~3.5, then add described adsorbent, make its concentration in mixed solution be controlled at 0.8g/L~2g/L, reaction 240min~300min, completes absorption.In this absorption system, plumbous main with electronegative PbEDTA
2-and PbHEDTA
-form exists, and the main existence form of zinc is Zn
2+, in this acid pH solution, the zeta current potential > 10mV of adsorbent.
In above-mentioned application, further, to the above-mentioned absorption completing after absorption, there are plumbous adsorbent and lead to recycle, comprise the following steps: (selective absorption lead is by electronegative PbEDTA in strongly acidic solution to have plumbous adsorbent to join the sodium hydroxide solution of 0.02mol/L~0.05mo/L absorption
2-and PbHEDTA
-and interact and carry out between the protonated adsorbent in surface, rising along with pH, adsorption capacity declines, belong to typical part adsorpting type, therefore select NaOH as actified solution) middle wash-out, it is 1g~1.5g that described absorption has the consumption of plumbous adsorbent in every liter of sodium hydroxide solution, then at room temperature shake 60min~90min, Magnetic Isolation goes out adsorbent, through cleaning to neutrality, obtains the adsorbent of regeneration; Repeatedly for adsorbing the wash-out that has plumbous adsorbent, until elution efficiency is less than 90%, make lead obtain enrichment the leaded sodium hydroxide solution obtaining after wash-out first.
In above-mentioned application, further, utilize the adsorbent of regeneration obtained above to adsorb the zinc of (lead is selectively adsorbed) in above-mentioned plumbous zinc binary metal solution, comprise the following steps: regulating the pH value of the plumbous plumbous zinc binary metal solution selectively having been adsorbed is 5.5~7, then add described adsorbent, make its concentration in mixed solution be controlled at 0.8g/L~2g/L
,reaction 240min~300min, completes absorption.
In above-mentioned various application, preferably, the zinc in described plumbous zinc binary metal solution and plumbous molar concentration equate.
Compared with prior art, advantage of the present invention is:
Performance of the adsorbent of the present invention is stable, easily separated fast from liquid phase, and can stablize at strong acid and highly basic magnetic, suitable various operating environments, and adsorbent can be regenerated by simple acid or alkali treatment in addition; The preparation method of this adsorbent, technique is simple, with low cost; The unexpected advantage of this adsorbent in selective absorption zinc and plumbous application is: selectively strong, can realize zinc and lead are almost reached to 100% selective absorption, greatly reduce difficulty and the cost of removal heavy metal operation in many metallic solutions, and the heavy metal of absorption can wash-out and obtained enrichment, be convenient to recycling.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the magnetic nanometer adsorbent of the imido grpup that makes of the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the magnetic nano-particle of the embodiment of the present invention 1;
Fig. 3 is the adsorbent design sketch to zinc and plumbous absorption under different EDTA concentration that utilizes embodiment 1 to make in the embodiment of the present invention 2 and embodiment 3;
Fig. 4 be in the embodiment of the present invention 3 under different EDTA concentration the zinc in plumbous zinc binary metal solution and plumbous ionic species distribution map;
Fig. 5 is the adsorbent design sketch to zinc and plumbous absorption under different pH values that utilizes embodiment 1 to make in the embodiment of the present invention 3 and embodiment 4;
Fig. 6 is the plumbous ionic species distribution map in the lower plumbous zinc binary metal solution of different pH values in the embodiment of the present invention 4;
Fig. 7 is the ionic species distribution map of the zinc in the lower plumbous zinc binary metal solution of different pH values in the embodiment of the present invention 4;
Fig. 8 is the adsorbent design sketch to zinc selective absorption under different plumbous zinc binary metal initial concentrations that utilizes embodiment 1 to make in the embodiment of the present invention 3;
Fig. 9 is the adsorbent design sketch to plumbous selective absorption under different plumbous zinc binary metal initial concentrations that utilizes embodiment 1 to make in the embodiment of the present invention 4;
Figure 10 utilizes the adsorbent that embodiment 1 makes to repeat (6 times) absorption zinc and plumbous design sketch in the invention process 3 and embodiment 4.
The specific embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is further illustrated.
embodiment 1:
A kind of magnetic nanometer adsorbent of imido grpup of the present invention as shown in Figure 1, this adsorbent is formed by magnetic nano-particle and polymine covalent cross-linking, the particle diameter of adsorbent is 60nm, magnetic nano-particle is obtained by nano ferriferrous oxide calcining, and the surface of magnetic nano-particle is formed with γ – Fe
2o
3.
A preparation method for above-mentioned adsorbent, comprises the following steps:
(1) prepare magnetic nano-particle: ferrous and 0.4mol ferric trichloride is configured to the mixed solution of 300mL by the dichloride of 0.2mol, then fill 15min nitrogen, remove the oxygen in solution, under 60 ℃ of water-baths and strong mechanical agitation, the ammonia spirit that adds 4mol/L, regulate pH in 11 left and right, after reaction 40min, centrifugal collection magnetic nanoparticle (nano ferriferrous oxide, particle diameter is 40nm) and repeatedly clean final vacuum and be dried and grind, by dried nano ferriferrous oxide 320 ℃ of calcining 60min in Muffle furnace, γ – Fe is contained on the surface that obtains chemical stability enhancing
2o
3the magnetic nano-particle (referring to Fig. 2) of rufous,
(2) covalent cross-linking: the concentration that magnetic nano-particle obtained above is joined to pH=10 is priming reaction 120min at 80 ℃ in 1.5 mol/L sodium laurate solution, after repeatedly cleaning with second alcohol and water, transfer to again volumetric concentration and be in 8% polyethyleneimine: amine aqueous solution that (utilizing volumetric concentration is 50% methanol aqueous solution polyethylene dissolving imines, thereby obtain volumetric concentration and be 8% polyethyleneimine: amine aqueous solution), under the water-baths of 80 ℃ and mechanical agitation, react 100min, after having reacted, obtain the magnetic nanometer adsorbent (referring to Fig. 1) of imido grpup.
embodiment 2: adsorbent adsorbs zinc and plumbous application in plumbous zinc binary metal solution simultaneously
To contain equimolar plumbi nitras and zinc nitrate (C
zn=C
pb=1mmol/L) binary heavy metal solution is divided into four groups, then add respectively the EDTA(0.1mmol/L of four groups of variable concentrations, 0.5mmol/L, 0.8mmol/L, 1mmol/L), make EDTA in every group of mixed solution and molar concentration rate≤0.5 of plumbous zinc metal ion, the pH value that regulates respectively again mixed solution is 6, and the adsorbent that then adds respectively embodiment 1 to make makes its concentration in every group of mixed solution be controlled at 2g/L, reaction 240min, completes absorption.
As shown in Figure 3, as seen from the figure, in EDTA and plumbous zinc binary metal solution, during molar concentration rate≤0.5 of plumbous zinc metal ion, adsorbent all has good adsorption effect to zinc and the lead in plumbous zinc binary metal solution to result.
embodiment 3: adsorbent is selected the application of absorption zinc in plumbous zinc binary metal solution
(1) under the condition of the EDTA of variable concentrations
To contain equimolar plumbi nitras and zinc nitrate (C
zn=C
pb=1mmol/L) binary metal solution is divided into five groups, then add respectively the EDTA(1.2mmol/L of five groups of variable concentrations, 1.4mmol/L, 1.6mmol/L, 1.8mmol/L, 2.0mmol/L), make the molar concentration rate of EDTA in every group of mixed solution and plumbous zinc metal ion in (0.6~1.0): in 1 scope, the pH value that regulates again mixed solution is 6, then the adsorbent that adds respectively embodiment 1 to make, make its concentration in every group of mixed solution be controlled at 2g/L, reaction 240min, completes absorption.
Result as shown in Figure 3, as seen from the figure, zinc in EDTA and the plumbous binary metal solution of zinc and plumbous molar concentration rate are (0.6~1.0): 1, adsorbent has good adsorption effect (now, hardly Adsorption of Lead) to the zinc in the plumbous binary metal solution of zinc, because, as shown in Figure 4, in mixed solution, lead is preferentially combined with EDTA, forms electronegative PbEDTA
2-, when lead is all converted into corresponding chelate, zinc is mainly with Zn
2+form exist, under the solution condition of pH=6, the adsorbent of imines functionalization is by forming coordinate bond and Zn
2+effect, rather than by electrostatic interaction and electronegative plumbous chelate effect.
(2) under the condition of different pH values
To contain equimolar plumbi nitras and zinc nitrate (C
zn=C
pb=1mmol/L) the plumbous binary metal solution of zinc is divided into ten groups, and then adding respectively concentration is that EDTA in every group of mixed solution of EDTA(of 1.4 mmol/L and the mol ratio of plumbous zinc metal ion are 0.7: 1), then to regulate respectively the pH value of mixed solution be 1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0, then the adsorbent that adds respectively embodiment 1 to make, make its concentration in every group of mixed solution be controlled at 2g/L, reaction 240min, completes absorption.
As shown in Figure 5, as seen from the figure, the pH value of mixed solution is 5.5~6 o'clock to result, and adsorbent has good adsorption effect (now, to plumbous adsorbance seldom) to the zinc in the plumbous binary metal solution of zinc.
(3) under the condition of Different Zinc initial concentration
Choose respectively the plumbous zinc binary metal solution (molar concentration plumbous and zinc equates) of some groups of Different Zinc initial concentrations (concentration range is 0.5 mmol/L~5 mmol/L), the EDTA that adds respectively variable concentrations, make the molar concentration rate 0.7: 1 of EDTA in every group of mixed solution and plumbous zinc metal ion, the pH value that regulates again mixed solution is 6, then the adsorbent that adds respectively embodiment 1 to make, make its concentration in every group of mixed solution be controlled at 2g/L, reaction 240min, complete absorption, result as shown in Figure 8, as seen from the figure, in the plumbous zinc binary metal solution of different zinc initial concentrations, adsorbent has higher selective absorption efficiency to zinc.
(4) recovery of adsorbent and zinc
There is the adsorbent of zinc to join wash-out in the hydrochloric acid solution that concentration is 0.05mol/L above-mentioned absorption, the consumption of the adsorbent that absorption has zinc in every liter of hydrochloric acid solution is 1g, then at room temperature shakes 80min, and Magnetic Isolation goes out adsorbent, through cleaning to neutrality, obtain the adsorbent of regeneration; The adsorbent obtaining through wash-out can reuse, the present embodiment has carried out 6 recyclings (absorption and wash-out), as shown in figure 10, as seen from the figure, the adsorbent of the 6th recycling still has good adsorption effect to zinc to the result of 6 adsorption-desorption cyclings.
By the hydrochloric acid solution containing zinc obtaining after above-mentioned wash-out first, repeatedly for adsorbing the wash-out of the adsorbent that has zinc, until elution efficiency is less than 90%, the zinc concentration of enrichment is up to 10mmol/L.
By the adsorbent of regeneration obtained above for adsorbing the lead of the plumbous zinc binary metal solution that above-mentioned zinc selectively adsorbed, comprise the following steps: the pH value of the plumbous zinc binary metal solution that adjusting zinc has selectively been adsorbed is 1.5~3.5, then the adsorbent that adds above-mentioned regeneration, make its concentration in mixed solution be controlled at 2g/L, reaction 240min, completes absorption.
embodiment 4: adsorbent is selected the application of Adsorption of Lead in plumbous zinc binary metal solution
(1) under the condition of different pH values
To contain equimolar plumbi nitras and zinc nitrate (C
zn=C
pb=1mmol/L) the plumbous binary metal solution of zinc is divided into ten groups, and then adding respectively concentration is that the EDTA of every group of mixed liquor of EDTA(and the mol ratio of plumbous zinc metal ion of 1.4 mmol/ is 0.7: 1), the pH value that then regulates respectively mixed solution is 1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0, the adsorbent that adds respectively embodiment 1 to make again, make its concentration in every group of mixed solution be controlled at 2g/L, reaction 240 min, complete absorption.
Result as shown in Figure 5, as seen from the figure, when the pH of mixed solution value is 1.5~3.5, adsorbent has good adsorption effect (now, to the adsorbance of zinc seldom) to the lead in the plumbous binary metal solution of zinc, especially the pH value of mixed solution is 2 o'clock, it is best that adsorption effect reaches, because, this and the ionic species distribution relevant (referring to Fig. 6 and Fig. 7) of plumbous and zinc, when pH=2, lead is mainly with PbEDTA
2-and PbHEDTA
-form exist, it is so Zn that the main existence form of zinc is appointed
2+, and the protonated degree of adsorbent surface very high (zeta current potential=11.2 mV) under this condition, the plumbous compound of therefore main adsorption band negative electrical charge.
(2) under the condition of different plumbous initial concentrations
Choose respectively the plumbous zinc binary metal solution (molar concentration plumbous and zinc equates) of some groups of different plumbous initial concentrations (concentration range is 0.5mmol/L~5mmol/L), then add respectively the EDTA of variable concentrations, make the molar concentration rate 0.7: 1 of EDTA in every group of mixed solution and plumbous zinc metal ion, the pH value that regulates again mixed solution is 2, then the adsorbent that adds respectively embodiment 1 to make, make its concentration in every group of mixed liquor be controlled at 2g/L, reaction 240min, complete absorption, result as shown in Figure 9, as seen from the figure, under different plumbous initial concentrations, adsorbent has higher selective absorption efficiency to lead.
(3) adsorbent and plumbous recovery
There is plumbous adsorbent to join wash-out in the sodium hydroxide solution of 0.04mol/L above-mentioned absorption, it is 1g that absorption has the consumption of plumbous adsorbent in every liter of sodium hydroxide solution, then at room temperature shakes 80min, and Magnetic Isolation goes out adsorbent, through cleaning to neutrality, obtain the adsorbent of regeneration; The adsorbent obtaining through wash-out can reuse, the present embodiment has carried out 6 recyclings (absorption and wash-out), as shown in figure 10, as seen from the figure, the adsorbent of the 6th recycling still has good adsorption effect to lead to the result of 6 adsorption-desorption cyclings.
By the leaded sodium hydroxide solution obtaining after above-mentioned wash-out first repeatedly for adsorbing the wash-out that has plumbous adsorbent, until elution efficiency is less than 90%, again to the plumbous wash-out in sodium hydroxide solution, thereby make lead obtain enrichment, plumbous concentration is up to 10 mmol/L.
By the adsorbent of regeneration obtained above for adsorbing the zinc of the plumbous zinc binary metal solution that above-mentioned lead selectively adsorbed, comprise the following steps: regulating the pH value of the plumbous plumbous zinc binary metal solution selectively having been adsorbed is 7, then the adsorbent that adds above-mentioned regeneration, makes its concentration in mixed solution be controlled at 2g/L
,reaction 240min, completes absorption.
Claims (8)
1. the preparation method of a magnetic nanometer adsorbent, it is characterized in that, described adsorbent is formed by magnetic nano-particle and polymine covalent cross-linking, and described magnetic nano-particle is mainly comprised of nano ferriferrous oxide, and the surface of described magnetic nano-particle is coated with one deck γ – Fe
2o
3particle, described preparation method comprises the following steps:
(1) prepare magnetic nano-particle: first synthesis of nano tri-iron tetroxide, then tri-iron tetroxide is calcined to 60min~80min at 300 ℃~350 ℃, obtain surface and be coated with one deck γ – Fe
2o
3the magnetic nano-particle of particle;
(2) covalent cross-linking: described magnetic nano-particle is joined in sodium laurate solution and activated, through cleaning separation, then transfer in polyethyleneimine: amine aqueous solution and carry out mechanical agitation reaction, obtain the magnetic nanometer adsorbent of imido grpup after having reacted;
In described step (2), the concentration of sodium laurate solution is 1mol/L~2mol/L, and pH value is 9~11, and soak time is 120min~150min, and activation temperature is 60 ℃~80 ℃; The volumetric concentration of polyethyleneimine: amine aqueous solution is 5%~8%, and mechanical agitation reaction temperature is 60 ℃~80 ℃, and the mechanical agitation reaction time is 90min~120min.
2. the magnetic nanometer adsorbent that a preparation method as claimed in claim 1 makes adsorbs zinc and plumbous application in plumbous zinc binary metal solution simultaneously, it is characterized in that, comprise the following steps: in plumbous zinc binary metal solution, add disodium ethylene diamine tetraacetate, the molar concentration rate that makes disodium ethylene diamine tetraacetate in mixed solution and plumbous zinc metal ion is (0~0.5): 1, and the addition of disodium ethylene diamine tetraacetate is not 0, the pH value that regulates again mixed solution is 6~7, then add described adsorbent, make its concentration in mixed solution be controlled at 0.8g/L~2g/L, reaction 240min~300min, complete absorption.
3. the magnetic nanometer adsorbent that a preparation method as claimed in claim 1 makes is selected the application of absorption zinc in plumbous zinc binary metal solution, it is characterized in that, comprise the following steps: in plumbous zinc binary metal solution, add disodium ethylene diamine tetraacetate, the molar concentration rate that makes disodium ethylene diamine tetraacetate in mixed solution and plumbous zinc metal ion is (0.6~1.0): 1, the pH value that regulates again mixed solution is 5.5~7, then add described adsorbent, make its concentration in mixed solution be controlled at 0.8g/L~2g/L
,reaction 240min~300min, completes absorption.
4. application according to claim 3, it is characterized in that, after completing absorption, adsorbent and zinc are recycled, comprise the following steps: have the adsorbent of zinc to join wash-out in the hydrochloric acid solution that concentration is 0.04mol/L~0.07mol/L absorption, the consumption of the adsorbent that described absorption has zinc in every liter of hydrochloric acid solution is 1g~1.5g, then at room temperature shakes 60min~90min, and Magnetic Isolation goes out adsorbent, through cleaning to neutrality, obtain the adsorbent of regeneration; Repeatedly for adsorbing the wash-out of the adsorbent that has zinc, until elution efficiency is less than 90%, make zinc obtain enrichment the hydrochloric acid solution containing zinc obtaining after wash-out first.
5. application according to claim 4, it is characterized in that, by the adsorbent of described regeneration for adsorbing the lead of the plumbous zinc binary metal solution that zinc selectively adsorbed, comprise the following steps: the pH value of the plumbous zinc binary metal solution that adjusting zinc has selectively been adsorbed is 1.5~3.5, then the adsorbent that adds described regeneration, make its concentration in mixed solution be controlled at 0.8g/L~2g/L, reaction 240min~300min, completes absorption.
6. the magnetic nanometer adsorbent that a preparation method as claimed in claim 1 makes is selected the application of Adsorption of Lead in plumbous zinc binary metal solution, it is characterized in that, comprise the following steps: in plumbous zinc binary metal solution, add disodium ethylene diamine tetraacetate, making disodium ethylene diamine tetraacetate in mixed solution and the molar concentration rate of plumbous zinc metal ion is 0.7: 1, the pH value that regulates again mixed solution is 1.5~3.5, then add described adsorbent, make its concentration in mixed solution be controlled at 0.8g/L~2g/L, reaction 240min~300min, completes absorption.
7. application according to claim 6, it is characterized in that, described adsorbent and the lead completing after absorption is recycled, comprise the following steps: have plumbous adsorbent to join wash-out in the sodium hydroxide solution of 0.02mol/L~0.05mo/L absorption, it is 1g~1.5g that described absorption has the consumption of plumbous adsorbent in every liter of sodium hydroxide solution, then at room temperature shakes 60min~90min, and Magnetic Isolation goes out adsorbent, through cleaning to neutrality, obtain the adsorbent of regeneration; Repeatedly for adsorbing the wash-out that has plumbous adsorbent, until elution efficiency is less than 90%, make lead obtain enrichment the leaded sodium hydroxide solution obtaining after wash-out first.
8. application according to claim 7, it is characterized in that, the zinc of the plumbous zinc binary metal solution that the adsorbent of described regeneration has selectively been adsorbed for Adsorption of Lead, comprise the following steps: regulating the pH value of the plumbous plumbous zinc binary metal solution selectively having been adsorbed is 5.5~7, then the adsorbent that adds described regeneration, makes its concentration in mixed solution be controlled at 0.8g/L~2g/L
,reaction 240min~300min, completes absorption.
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