CN102872790A - Sulfate radical sorbent magnetic nanometer zirconium hydroxide and preparation method thereof - Google Patents
Sulfate radical sorbent magnetic nanometer zirconium hydroxide and preparation method thereof Download PDFInfo
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- CN102872790A CN102872790A CN2012103575139A CN201210357513A CN102872790A CN 102872790 A CN102872790 A CN 102872790A CN 2012103575139 A CN2012103575139 A CN 2012103575139A CN 201210357513 A CN201210357513 A CN 201210357513A CN 102872790 A CN102872790 A CN 102872790A
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Abstract
The invention relates to a sulfate radical sorbent magnetic nanometer zirconium hydroxide and a preparation method thereof. The preparation method comprises the following steps: (1), modifying magnetic Fe3O4 nanoparticles; (2), under mechanical stirring, firstly, quickly dripping a ZrOC12 solution in a Fe3O4 suspending liquid, then slowly dripping an ammonia solution until the pH value is 9-10, followed by standing and aging so as to obtain wet sol sedimentation, and finally performing sedimentation washing and suction filtration; and (3), dissolving the wet sol in a n-butanol for azeotropic distillation, vacuum drying after the termination of the distillation, and extracting for grinding and sieving so as to obtain the sulfate radical sorbent magnetic nanometer zirconium hydroxide. According to the invention, the solid-liquid separation is easily realized after the adsorption of the sulfate radical sorbent; the magnetic field solid-liquid separation is simpler and convenient; and the water basically has no residual after the sulfate radical is desorbed, and the adsorption effect is good.
Description
Technical field
The present invention relates to a kind of adsorbent of removing sulfate radical in the water body, relate in particular to a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide and preparation method thereof.
Background technology
Sulfate wastewater extensively is present in the industrial production such as mine, metallurgy and chemical industry, pharmacy, food, printing and dyeing.High concentration sulfate under anaerobic is converted into hydrogen sulfide or sulfo-sulfide etc. by sulfate reducing bacteria, directly is detrimental to health and the ecological balance.The hydrogen sulfide meeting heavy corrosion pipeline that containing sulfate waste water produces simultaneously can scale effect production in industrial production.The existence of sulfate can suppress anaerobe, increases the wastewater biochemical intractability.Therefore develop a kind of clearance adsorbent high, cheap and that can reuse significant for removing sulfate radical.The sulfate radical technique that removes of comparative maturity has at present: freezing; Chemical precipitation method; Ion-exchange; Membrane separation process.Often energy consumption is large, cost is high for freezing.In the chemical precipitation method, the calcium chloride poor removal effect; The barium chloride use cost is high and toxic; It is longer that brium carbonate is removed the sulfate radical time, and easy blocking pipe.Ion-exchange and membrane separation process investment are all relatively high.Absorption method can more and more be paid attention to because of simple to operate, effective and adsorbent in regeneration.Zirconium hydroxide has the advantages such as clearance is high, avirulence, operation is simple, the adsorption and desorption reaction rate is fast in the removing of sulfate radical, but shortcoming is the Separation of Solid and Liquid difficulty.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the problems of the prior art, a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide and preparation method thereof is provided, be easy to Separation of Solid and Liquid after this sulfate radical adsorbent absorption, adopt the magnetic field Separation of Solid and Liquid more simple and convenient, can effectively guarantee water body noresidue after removing sulfate radical, advantages of good adsorption effect.
The present invention is in order to solve the problems of the technologies described above, and the technical scheme that adopts is:
A kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide, it prepares in accordance with the following steps:
(1) modification of magnetic ferroferric oxide nano-particles: the ratio according to ferriferrous oxide nano-particle and sodium citrate solution is 1g:(40～80) mL, nano ferriferrous oxide is joined in the 0.2mol/L sodium citrate solution, elder generation's ultrasonic wave disperses 30～40min, constant-temperature table shakes 15～30min again, magnetic is isolated the magnetic ferroferric oxide nano-particles after the modification, uses absolute ethanol washing, then is transferred in the container, add deionized water, namely get water base Fe
3O
4Suspension;
(2) in tri-iron tetroxide suspension, add polyethylene glycol, dissolving; Then under the condition of 59～61 ℃ of bath temperatures, mixing speed 900～1200rpm, drip fast 0.5mol/L ZrOCl
2Solution, ZrOCl
2The addition of solution is according to ZrOCl
2And Fe
3O
4Mol ratio is (3～11): 1 determines; Drip ammonia spirit at a slow speed again until pH stopped to drip at 9 ~ 10 o'clock; Leave standstill aging 30min, obtain sol precipitation, magnetic is isolated solid product, with the deionized water cyclic washing until pH be neutrality and can't detect Cl
-, last suction filtration obtains filter cake;
(3) in filter cake, inject the long-pending n-butanol of decaploid, after the mixing making beating evenly, will obtain ZrO (OH)
2/ Fe
3O
4Wet colloidal sol carries out azeotropic distillation to remove moisture; End final vacuum to be distilled is dry, grinds after taking out and sieves, and namely gets sulfate radical adsorbent magnetic Nano zirconium hydroxide.
Press such scheme, the quality of the described polyethylene glycol of step (2) is ZrOCl
2(3～6) % of quality.
Press such scheme, the speed of the described quick dropping of step (2) is (7～9) mL/min.
Press such scheme, the described speed that drips at a slow speed of step (2) is (2～3) mL/min.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention is with water base Fe
3O
4Suspension is matrix, ZrOCl
2Solution and ammonia spirit are raw material, adopt sol-gal process synthesizing magnetic nanometer zirconium hydroxide, be easy to Separation of Solid and Liquid after this sulfate radical adsorbent absorption, adopt the magnetic field Separation of Solid and Liquid more simple and convenient, can effectively guarantee water body substantially not residual adsorbent after removing sulfate radical;
When (2) the sulfate radical adsorbent magnetic Nano zirconium hydroxide for preparing of the present invention was applied to remove sulfate radical in the water body, clearance and adsorption capacity can reach respectively 89.97% and 112.47mg/g; Adsorbent still had preferably adsorption effect after regeneration was processed;
(3) the present invention is with ZrO (OH)
2/ Fe
3O
4Wet colloidal sol dewaters in the mode of azeotropic distillation, further reduces agglomeration, has increased the specific area of magnetic Nano zirconium hydroxide, more easily adsorbs a large amount of sulfate radicals, thereby better removes the sulfate ion in the water body;
(4) the present invention makes its dispersion stabilization better through the improved ferroferric oxide nano particle, has reduced reunion, has improved nanometer Fe
3O
4Utilization rate;
(5) whole preparation process is simple, does not need harsh consersion unit, condition.
Description of drawings
Fig. 1 is Fourier infrared spectrum (FT-IR) spectrogram of the sulfate radical adsorbent magnetic Nano zirconium hydroxide for preparing of the embodiment of the invention 1.
Fig. 2 be the sulfate radical adsorbent magnetic Nano zirconium hydroxide of embodiment 1 preparation when using the initial pH of solution on the impact of removal effect.
Fig. 3 be the sulfate radical adsorbent magnetic Nano zirconium hydroxide of embodiment 1 preparation when using the initial pH of solution be that 1.5 o'clock adsorbent dosages are to SO
4 2-The impact of removal effect.
Fig. 4 be the sulfate radical adsorbent magnetic Nano zirconium hydroxide of embodiment 2 preparation when using the initial pH of solution be that 2 o'clock adsorbent dosages are to SO
4 2-The impact of removal effect.
Fig. 5 be the sulfate radical adsorbent magnetic Nano zirconium hydroxide of embodiment 2 preparation when using the adsorbent reactivation number of times to SO
4 2-The impact of adsorption capacity.
Fig. 6 is that the sulfate radical adsorbent magnetic Nano zirconium hydroxide of embodiment 3 preparations is to the adsorption isotherm of sulfate radical simulated wastewater.
The sulfate radical adsorbent magnetic Nano zirconium hydroxide that Fig. 7,8 is respectively embodiment 1 preparation to the absorption of sulfate radical simulated wastewater after magnetic separate before and after design sketch.
Fig. 9 is transmission electron microscope (TEM) figure of the sulfate radical adsorbent magnetic Nano zirconium hydroxide for preparing of the present invention.
The specific embodiment
For understanding better the present invention, below in conjunction with embodiment content of the present invention is further illustrated, but the present invention not only is confined to the following examples.
The used ferriferrous oxide nano-particle of the present invention can adopt the liquid-phase coprecipitation preparation, concrete steps are as follows: with the divalent salts of iron and trivalent salt by 1: 1.75～2(mol ratio) add in the container and mix, logical nitrogen protection, be positioned over 65 ± 1 ℃ of waters bath with thermostatic control, speed with 900～1200rpm stirs simultaneously the at a slow speed pure ammoniacal liquor of dropping analysis, until pH remains on 9-10, continue constant temperature and stir crystallization 30min, obtain black suspension; Magnetic is isolated sediment, is neutral with the deionized water cyclic washing to pH, and sediment is placed 60 ℃ of lower dry 12h of vacuum drying chamber, and grinding is also crossed 200 mesh sieves, namely gets magnetic Fe
3O
4Nano particle.Wherein, the divalent salt solutions of iron can be FeSO
4, FeCl
2Deng solution, the trivalent salting liquid of iron can be Fe
2(SO
4)
3, FeCl
3Deng solution.
Certainly, commercially available nano ferriferrous oxide also can be applied to the present invention, and used among the embodiment 2 is Aladdin reagent Co., Ltd, and purity is 99.5%, 20nm, sphere.
Embodiment 1:
A kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide, it prepares in accordance with the following steps:
(1) takes by weighing 0.5262g Fe
3O
4Nano particle joins ultrasonic wave dispersion 40min in the 40mL0.2mol/L sodium citrate solution, shakes 30min again, magnetic is isolated the Nanometer Magnetite after the modification, behind absolute ethanol washing 2 times, is transferred to there-necked flask, add again the 20mL deionized water, be water base Fe
3O
4Suspension;
(2) to Fe
3O
4Add the 0.2674g polyethylene glycol in the suspension, dissolving; When 60 ℃ of bath temperatures, mixing speed 900rpm, drip 50mL0.5mol/LZrOCl with 9mL/min
2Solution drips at a slow speed the 2mol/L ammonia spirit with 3mL/min again, stops to drip until pH remains at 10 o'clock; Leave standstill aging 30min, obtain sol precipitation, magnetic is isolated solid product, until pH is neutrality, and can't detect Cl with the deionized water cyclic washing
-, last suction filtration obtains filter cake;
(3) in filter cake, inject the 300mL n-butanol, after the mixing making beating evenly, carry out azeotropic distillation.After the end to be distilled, in 120 ℃ of vacuum drying 12h, take out and grind, cross 200 mesh sieves, namely get sulfate radical adsorbent magnetic Nano zirconium hydroxide.
ZrOCl when the present embodiment prepares the magnetic Nano zirconium hydroxide
2And Fe
3O
4Mol ratio is 11:1.
Fourier infrared spectrum as shown in Figure 1,452.96cm
-1Characteristic absorption peak is the Zr-O key, 3422.25cm
-1Absworption peak is the stretching vibration absworption peak of four kinds of different hydroxyls, 1627.76cm
-1Absworption peak is the hydroxyl flexural vibrations absworption peak of physical absorption water and structure water of coordination, 1351.36 cm
-1Absworption peak is O-H bond bending vibration absorption peak.Above analysis as can be known, the product for preparing is sulfate radical adsorbent magnetic Nano zirconium hydroxide.
Primary condition during application: get the metabisulfite solution that 50mL concentration is 1000mg/L, be adjusted to different initial pH with 2.0mol/LHCl solution, placing freezing thermostat oscillator to temperature is 40 ℃, add a certain amount of magnetic Nano zirconium hydroxide, concussion absorption 30min under the 220r/min speed, then the magnetic Nano zirconium hydroxide is removed in the magnetic separation, gets supernatant and measures sulfate concentration.Selecting 50mL, 0.1mol/LNaOH during adsorbent reactivation is desorbing agent.
Sulfate radical adopts Barium Chromate Spectrophotometry to measure, and removing efficient and adsorption capacity can be calculated as follows.
In the formula: η is that sulfate radical is removed efficient; Q is adsorbance (mg/g); C
oAnd C
eBe respectively before the absorption and sulfate concentration (mg/L) after the absorption; V is liquor capacity (mL); The magnetic Nano zirconium hydroxide quality (g) of m for adding.
As shown in Figure 2, when the sulfate radical adsorbent magnetic Nano zirconium hydroxide dosage of embodiment 1 preparation is 0.4g, clearance and adsorption capacity all descend with the increase of the initial pH of metabisulfite solution, and wherein pH increases at 2 o'clock, clearance and adsorption capacity slow decreasing from 1; PH from 2 to 3 o'clock descends rapidly; Increase after pH arrives 3, clearance and adsorption capacity maintain reduced levels and no longer change again.But it is better little to be not that pH is healed, and pH is less than after 1, and the magnetic zirconium hydroxide can neutralization reaction occur with acid and dissolve, thereby causes the magnetic Nano zirconium hydroxide to run off.Therefore best pH scope is 1～2.
Fig. 3 is that the initial pH of adjusting metabisulfite solution is 1.5 o'clock, and the adsorbent magnetic Nano zirconium hydroxide dosage of embodiment 1 preparation and the relation of clearance and adsorption capacity are along with the increase clearance rising of adsorbent dosage, progressively stable at last; When dosage was 0.4g, clearance and adsorption capacity were respectively 89.97%, 112.47mg/g.
Fig. 7,8 be the sulfate radical adsorbent magnetic Nano zirconium hydroxide of embodiment 1 preparation to the absorption of sulfate radical simulated wastewater after magnetic separate before and after the vision design sketch, be easy to Separation of Solid and Liquid after can finding out the absorption of sulfate radical adsorbent, adopt the magnetic field Separation of Solid and Liquid more simple and convenient, can effectively guarantee water body substantially not residual adsorbent after removing sulfate radical.
Embodiment 2:
A kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide, it prepares in accordance with the following steps:
(1) modification of magnetic ferroferric oxide nano-particles: take by weighing the Fe that embodiment 1 prepares
3O
4Nano particle 0.8269g joins ultrasonic wave dispersion 30min in the 50mL0.2mol/L sodium citrate solution, shakes 15min again, magnetic is isolated the magnetic ferroferric oxide nano-particles after the modification, behind absolute ethanol washing 2 times, is transferred to there-necked flask, add again the 20mL deionized water, be water base Fe
3O
4Suspension;
(2) to water base Fe
3O
4Add the 0.2087g polyethylene glycol in the suspension, dissolving.Under 60 ℃ of bath temperatures, mixing speed 1000rpm, drip 50mL0.5mol/LZrOCl with 7.5mL/min
2Solution drips at a slow speed the 2mol/L ammonia spirit with 2.5mL/min again, stops to drip until pH remains at 10 o'clock; Leave standstill aging 30min, obtain sol precipitation, magnetic is isolated solid product, until pH is neutrality, and can't detect Cl with the deionized water cyclic washing
-, last suction filtration obtains filter cake;
(3) in filter cake, inject the 300mL n-butanol, after the mixing making beating evenly, will obtain ZrO (OH)
2/ Fe
3O
4Wet colloidal sol carries out azeotropic distillation to remove moisture; End final vacuum to be distilled is dry, takes out and grinds, and crosses 200 mesh sieves, namely gets sulfate radical adsorbent magnetic Nano zirconium hydroxide.
ZrOCl when the present embodiment prepares the magnetic Nano zirconium hydroxide
2And Fe
3O
4Mol ratio is 7:1.
Characterize through Fourier infrared spectrum, the product for preparing is sulfate radical adsorbent magnetic Nano zirconium hydroxide.
Use: it is 2 that the primary condition when the present embodiment is used and embodiment 1 different are to regulate the initial pH of metabisulfite solution, the adsorbent magnetic Nano zirconium hydroxide dosage of embodiment 2 preparations is 0.1-0.7g, as shown in Figure 4, when dosage was 0.3g, clearance and adsorption capacity were respectively 58.35%, 97.25mg/g; As shown in Figure 5, be 2 at the initial pH of metabisulfite solution, when the adsorbent dosage is 0.3g, along with the increase of regeneration times, adsorption capacity can descend slightly to some extent again, after the 5th regeneration, adsorption capacity is 79.61mg/g, illustrates that the rear adsorbent of regeneration processing still has preferably adsorption effect.
Embodiment 3:
Magnetic Fe
3O
4The preparation of nano particle: the copperas solution of 0.5mol/L and the ferric chloride solution of 0.5mol/L were added in the there-necked flask in 1: 1.75 in molar ratio, pass into nitrogen, be positioned in 65 ℃ of thermostat water baths, 1200rpm stirs to drip at a slow speed simultaneously and analyzes pure ammoniacal liquor, remaining at 9 o'clock to pH stops to drip, continue constant temperature and stir 30min, obtain black suspension, after magnetic is isolated sediment, be neutral with the deionized water cyclic washing to pH, in 60 ℃ of dry 12h of lower vacuum drying, grinding is also crossed 200 mesh sieves, namely gets Fe with sediment
3O
4Nano particle.
A kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide, it prepares in accordance with the following steps:
(1) modification of magnetic ferroferric oxide nano-particles: take by weighing the above-mentioned Fe for preparing of 1.9294g
3O
4Nano particle joins ultrasonic dispersion 30min in the 80mL0.2mol/L sodium citrate solution, shakes 15min again, magnetic is isolated the Nanometer Magnetite after the modification, behind absolute ethanol washing 2 times, is transferred to there-necked flask, add again the 20mL deionized water, be water base Fe
3O
4Suspension;
(2) to water base Fe
3O
4Add the 0.1327g polyethylene glycol in the suspension, dissolving; Then under 60 ℃ of bath temperatures, mixing speed 1200rpm, drip 50mL0.5mol/LZrOCl with 7mL/min
2Solution drips at a slow speed the 2mol/L ammonia spirit with 2mL/min again, stops to drip until pH remains at 9 o'clock; Leave standstill aging 30min, obtain sol precipitation, magnetic is isolated solid product, until pH is neutrality, and can't detect Cl with the deionized water cyclic washing
-, last suction filtration obtains filter cake;
(3) in filter cake, inject the 300mL n-butanol, after the mixing making beating evenly, will obtain ZrO (OH)
2/ Fe
3O
4Wet colloidal sol carries out azeotropic distillation to remove moisture; After the end to be distilled, in 120 ℃ of vacuum drying 12h, take out and grind, cross 200 mesh sieves, namely get sulfate radical adsorbent magnetic Nano zirconium hydroxide.
ZrOCl when the present embodiment prepares the magnetic Nano zirconium hydroxide
2And Fe
3O
4Mol ratio is 3:1.
Characterize through Fourier infrared spectrum, the product for preparing is sulfate radical adsorbent magnetic Nano zirconium hydroxide.
Use: the primary condition when the present embodiment is used is from the different of embodiment 1: the initial pH of metabisulfite solution is 1.5, adsorbent dosage 0.4g.According to sulfate radical balance mass concentration C e and equilibrium adsorption capacity Qe after the absorption, the adsorption isotherm when doing respectively 30 ℃, 40 ℃, 50 ℃, 60 ℃, adsorbance slightly increases with the rising of temperature, shows that the rising temperature is favourable to adsorbing.When 30 ℃ of temperature, 40 ℃, 50 ℃, 60 ℃ the time, the maximum saturation adsorption capacity is respectively 117.64mg/g, 120.07mg/g, 121.71mg/g, 124.02mg/g.
In sum, pH is larger on the adsorbent impact, and suitable pH scope is 1 ~ 2; Clearance and adsorption capacity increase with dosage; When initial pH is 1.5, the sulfate radical initial concentration is that the 1000mg/L dosage is 8g/L, and clearance and adsorption capacity are respectively 89.97% and 112.47mg/g; Adsorbent still had preferably adsorption effect after regeneration was processed; Temperature during the rising adsorption reaction more is conducive to improve the magnetic Nano zirconium hydroxide to the adsorption effect of sulfate radical in the water body; Be easy to Separation of Solid and Liquid after the absorption of sulfate radical adsorbent, can effectively guarantee water body substantially not residual adsorbent after removing sulfate radical.
Claims (8)
1. sulfate radical adsorbent magnetic Nano zirconium hydroxide is characterized in that it prepares in accordance with the following steps:
(1) modification of magnetic ferroferric oxide nano-particles: the ratio according to ferriferrous oxide nano-particle and sodium citrate solution is 1g: (40～80) mL, nano ferriferrous oxide is joined in the 0.2mol/L sodium citrate solution, elder generation's ultrasonic wave disperses 30～40min, constant-temperature table shakes 15～30min again, magnetic is isolated the magnetic ferroferric oxide nano-particles after the modification, uses absolute ethanol washing, then is transferred in the container, add deionized water, namely get water base Fe
3O
4Suspension;
(2) in tri-iron tetroxide suspension, add polyethylene glycol, dissolving; Then under the condition of 59～61 ℃ of bath temperatures, mixing speed 900～1200rpm, drip fast ZrOCl
2Solution, ZrOCl
2The addition of solution is according to ZrOCl
2And Fe
3O
4Mol ratio is (3～11): 1 determines; Drip ammonia spirit at a slow speed again until pH stopped to drip at 9 ~ 10 o'clock; Leave standstill aging 30min, obtain sol precipitation, magnetic is isolated solid product, with the deionized water cyclic washing until pH be neutrality and can't detect Cl
-, last suction filtration obtains filter cake;
(3) in filter cake, inject the long-pending n-butanol of decaploid, after the mixing making beating evenly, will obtain ZrO (OH)
2/ Fe
3O
4Wet colloidal sol carries out azeotropic distillation to remove moisture; After the end to be distilled, vacuum drying is ground after taking out and is sieved, and namely gets sulfate radical adsorbent magnetic Nano zirconium hydroxide.
2. a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide according to claim 1 is characterized in that the quality of the described polyethylene glycol of step (2) is ZrOCl
2(3～6) % of quality.
3. a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide according to claim 1 is characterized in that the speed of the described quick dropping of step (2) is (7～9) mL/min.
4. a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide according to claim 1 is characterized in that the described speed that drips at a slow speed of step (2) is (2～3) mL/min.
5. the preparation method of a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide claimed in claim 1 is characterized in that it comprises the steps:
(1) modification of magnetic ferroferric oxide nano-particles: the ratio according to ferriferrous oxide nano-particle and sodium citrate solution is 1g:(40～80) mL, nano ferriferrous oxide is joined in the 0.2mol/L sodium citrate solution, elder generation's ultrasonic wave disperses (30～40) min, constant-temperature table shakes (15～30) min again, magnetic is isolated the magnetic ferroferric oxide nano-particles after the modification, uses absolute ethanol washing, then is transferred in the container, add deionized water, namely get water base Fe
3O
4Suspension;
(2) in tri-iron tetroxide suspension, add polyethylene glycol, dissolving; Then under the condition of 59～61 ℃ of bath temperatures, mixing speed 900～1200rpm, drip fast ZrOCl
2Solution, ZrOCl
2The addition of solution is according to ZrOCl
2And Fe
3O
4Mol ratio is (3～11): 1 determines; Drip ammonia spirit at a slow speed again until pH stopped to drip at 9 ~ 10 o'clock; Leave standstill aging 30min, obtain sol precipitation, magnetic is isolated solid product, with the deionized water cyclic washing until pH be neutrality and can't detect Cl
-, last suction filtration obtains filter cake;
(3) in filter cake, inject the long-pending n-butanol of decaploid, after the mixing making beating evenly, will obtain ZrO (OH)
2/ Fe
3O
4Wet colloidal sol carries out azeotropic distillation to remove moisture; End final vacuum to be distilled is dry, grinds after taking out and sieves, and namely gets sulfate radical adsorbent magnetic Nano zirconium hydroxide.
6. the preparation method of a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide according to claim 5 is characterized in that the addition of the described polyethylene glycol of step (2) is ZrOCl
2(3～6) % of quality.
7. the preparation method of a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide according to claim 5 is characterized in that the speed of the described quick dropping of step (2) is (7～9) mL/min.
8. the preparation method of a kind of sulfate radical adsorbent magnetic Nano zirconium hydroxide according to claim 5 is characterized in that the described speed that drips at a slow speed of step (2) is (2～3) mL/min.
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