CN104275145A - Preparation method of magnetic zirconium hydroxide adsorbent for absorbing fluorine ions - Google Patents

Preparation method of magnetic zirconium hydroxide adsorbent for absorbing fluorine ions Download PDF

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CN104275145A
CN104275145A CN201410534792.0A CN201410534792A CN104275145A CN 104275145 A CN104275145 A CN 104275145A CN 201410534792 A CN201410534792 A CN 201410534792A CN 104275145 A CN104275145 A CN 104275145A
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magnetic
zirconium hydroxide
preparation
zrocl
adsorbent
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李念
谢雄
王洪
杨鉴
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Wuhan Iron and Steel Group Corp
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    • 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
    • B01J20/02—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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a preparation method of a magnetic zirconium hydroxide adsorbent for absorbing fluorine ions. The method comprises the following steps: (1) adding nano-sized Fe3O4 into sodium citrate solution, firstly carrying out ultrasonic dispersion, then oscillating by a constant temperature shaking table, and carrying out magnetic separation to obtain modified magnetic Fe3O4 nano particles; (2) preparing the modified magnetic Fe3O4 nano particles into water-based Fe3O4 suspension; (3) obtaining sol precipitate from the water-based Fe3O4 suspension, carrying out magnetic separation to obtain the solid product, and finally carrying out suction filtration to obtain a filter cake; (4) carrying out azeotropic distillation on the obtained ZrO (OH)2/ Fe3O4 wet sol to remove water; then, carrying out vacuum drying, taking out, grinding and sieving to obtain the magnetic zirconium hydroxide adsorbent for absorbing the fluorine ions. After the preparation method of the magnetic zirconium hydroxide adsorbent for absorbing the fluorine ions is used, the adsorbent is easily subjected to solid-liquid separation when used for absorbing; the magnetic field solid-liquid separation is simpler and more convenient, no residue exits in the water after the fluorine ions of the water are removed, and the absorption effect of the magnetic zirconium hydroxide adsorbent is good.

Description

For the preparation method of the magnetic zirconium hydroxide adsorbent of Adsorption of fluoride ion
Technical field
The present invention relates to chemical industry technical field of smelting, particularly refer to a kind of preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion.
Background technology
The source of fluoride pollution is mainly from the emission produced in the processing of the smelting of aluminium, rock phosphate in powder, the production of phosphate fertilizer, the smelting of iron and steel and coal burning process.In its natural state, soil, seawater, the surface water, underground water all contain a certain amount of fluorine.Resident drinks high fluorine groundwater for a long time, there will be the fluorine poisoning symptom of tooth and bone, and this is by healthy for direct harmful to human.The present invention is intended to the novel magnetic zirconium hydroxide adsorbent developing a kind of Adsorption of fluoride ion, and is applied to the improvement occasion of fluoride waste, adopts magnetic field Separation of Solid and Liquid will be more simple and convenient, effectively can ensure water body noresidue after removing fluorine ion, advantages of good adsorption effect.
Fluoride waste is extensively present in the industrial production such as Ferrous Metallurgy, production of phosphate fertilizer, rock phosphate in powder processing, and in its natural state, soil, seawater, the surface water, underground water all contain a certain amount of fluorine.The fluorine ion technique that removes of current comparative maturity has: ion-exchange; The precipitation method; Dialysis; Electroosmose process; Absorption method.In the precipitation method, fluoride ion removing weak effect, can only as the pretreatment of drinking water defluorination; Ion-exchange and membrane separation process are invested all relatively high.Absorption method because of simple to operate, effective and adsorbent can regeneration and more and more being paid attention to.Zirconium hydroxide have in the removing of fluorine ion clearance high, non-toxic, run the advantages such as simple, adsorption and desorption reaction rate is fast, but shortcoming is Separation of Solid and Liquid difficulty.
All the time, the removal of fluorine ions in water body is one of water treatment study hotspot and difficult point.Fluorine ion except method various, but often kind of method all has the limitation of himself.Absorption method is because of simple to operate, advantages of good adsorption effect and adsorbent can regeneration and more and more being paid attention to.
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 preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion is provided, Separation of Solid and Liquid is easy to after this adsorbent, adopt magnetic field Separation of Solid and Liquid more simple and convenient, effectively can ensure water body noresidue after removing fluorine ion, advantages of good adsorption effect.
For achieving the above object, the preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion provided by the present invention, it comprises the steps:
(1) be 1g:(50 ~ 80 according to the ratio of ferriferrous oxide nano-particle and sodium citrate solution) mL, nano ferriferrous oxide being joined concentration is in the sodium citrate solution of 0.2 ~ 0.25mol/L, first ultrasonic wave dispersion 20 ~ 30min, constant-temperature table concussion 20 ~ 30min again, Magneto separate goes out modified magnetic ferroferric oxide nano-particles;
(2) by modified magnetic ferroferric oxide nano-particles absolute ethanol washing, be then transferred in container, add deionized water, obtain water base Fe 3o 4suspension;
(3) to water base Fe 3o 4add polyethylene glycol in suspension to dissolve; Then, under the condition of bath temperature 59 ~ 61 DEG C, mixing speed 900 ~ 1200rpm, fast drop concentration is the ZrOCl of 0.4 ~ 0.5mol/L 2solution, ZrOCl 2the addition of solution is ZrOCl 2and Fe 3o 4mol ratio is 3 ~ 11:1; Drip at a slow speed the ammonia spirit that concentration is 1.5 ~ 2mol/L again until stop when pH is 9 ~ 10 dripping; Leave standstill aging 30min, obtain sol precipitation, Magneto separate goes out solid product, with deionized water cyclic washing until pH is neutral and can't detect Cl -, last suction filtration obtains filter cake;
(4) in filter cake, the n-butanol of 8 ~ 10 times of volumes is injected, after mixing making beating evenly, by the ZrO (OH) obtained 2/ Fe 3o 4wet colloidal sol carries out azeotropic distillation to remove moisture; End final vacuum to be distilled is dry, and after taking out, grinding is sieved, and obtains fluorine ion absorber magnetic zirconium hydroxide.
As a kind of preferred version, in described step (1), be 1g:60mL according to the ratio of ferriferrous oxide nano-particle and sodium citrate solution, nano ferriferrous oxide being joined concentration is in the sodium citrate solution of 0.25mol/L, ultrasonic dispersing time is 25min, and the constant-temperature table concussion time is 25min.
As another preferred version, in described step (3), the quality of the polyethylene glycol of interpolation is ZrOCl 23 ~ 6% of quality; The ZrOCl of fast drop 0.5mol/L 2solution, rate of addition is 7 ~ 9mL/min; Drip at a slow speed the ammonia spirit of 2mol/L, rate of addition is 2 ~ 3mL/min.
As another preferred version, in described step (3), to water base Fe 3o 4add polyethylene glycol in suspension to dissolve; Bath temperature is 60 DEG C, mixing speed is 1000rpm, ZrOCl 2the addition of solution is ZrOCl 2and Fe 3o 4mol ratio is 8:1.
As another preferred version, in described step (4), in filter cake, inject the n-butanol of 10 times of volumes.
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 adsorbent fluorine ion, adopt magnetic field Separation of Solid and Liquid more simple and convenient, effectively can ensure water body substantially not residual adsorbent after removing fluorine ion;
(2), when the fluorine ion absorber magnetic zirconium hydroxide that the present invention prepares is applied in water body and removes fluorine ion, clearance and adsorption capacity can reach 95.3% and 192.47mg/g respectively; After regeneration process, adsorbent still has good adsorption effect;
(3) the present invention is by ZrO (OH) 2/ Fe 3o 4wet colloidal sol dewaters in the mode of azeotropic distillation, reduces agglomeration further, increases the specific area of magnetic zirconium hydroxide, more easily adsorb a large amount of fluorine ions, thus better removes the fluorine ion in water body;
(4) the present invention is through improved ferroferric oxide nano particle, makes its dispersion stabilization better, decreases reunion, improve nanometer Fe 3o 4utilization rate;
(5) whole preparation process is simple, does not need harsher consersion unit, condition.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
As shown in the figure, the present invention's ferriferrous oxide nano-particle used can adopt liquid-phase coprecipitation to prepare, concrete steps are as follows: the divalent salts of iron and trivalent salt added in container by 1:1.75 ~ 2 (mol ratio) and mix, logical nitrogen protection, be positioned over 65 ± 1 DEG C of waters bath with thermostatic control, stir to drip at a slow speed with the speed of 900 ~ 1200rpm simultaneously and analyze pure ammoniacal liquor, until pH remains on 9 ~ 10, continue constant temperature and stir crystallization 30min, obtain black suspension; Magneto separate goes out sediment, is neutral with deionized water cyclic washing to pH, sediment is placed in dry 12h at vacuum drying chamber 60 DEG C, grinds and cross 200 mesh sieves, obtaining 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.
Meanwhile, commercially available nano ferriferrous oxide also can be applied to the present invention, also have chosen the nano ferriferrous oxide that Aladdin reagent Co., Ltd is commercially available in the embodiment of the present invention, and purity is 99.5%, 20nm, spherical.
Embodiment one:
The preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion of the present invention, concrete steps are as follows:
(1) 0.5g Fe is taken 3o 4nano particle, joins ultrasonic wave dispersion 20min in 40mL0.2mol/L sodium citrate solution, then shakes 30min, Magneto separate goes out modified Nanometer Magnetite, after absolute ethanol washing 2 times, is transferred to there-necked flask, add 20mL deionized water again, be water base Fe 3o 4suspension;
(2) to Fe 3o 4add 0.2674g polyethylene glycol in suspension, dissolve; When bath temperature 60 DEG C, mixing speed 900rpm, drip 50mL0.5mol/LZrOCl with 9mL/min 2solution, then drip at a slow speed 2mol/L ammonia spirit with 3mL/min, until stop dripping when pH remains 10; Leave standstill aging 30min, obtain sol precipitation, Magneto separate goes out solid product, with deionized water cyclic washing until pH is neutral, and can't detect Cl -, last suction filtration obtains filter cake;
(3) in filter cake, inject 300mL n-butanol, after mixing making beating evenly, carry out azeotropic distillation.After end to be distilled, in 120 DEG C of vacuum drying 12h, take out grinding, cross 200 mesh sieves, obtain fluorine ion absorber magnetic Nano zirconium hydroxide.
ZrOCl when the present embodiment prepares magnetic Nano zirconium hydroxide 2and Fe 3o 4mol ratio is 11:1.
Embodiment two:
The preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion of the present invention, concrete steps are as follows:
(1) 1g Fe is taken 3o 4nano particle, joins ultrasonic wave dispersion 30min in 50mL0.25mol/L sodium citrate solution, then shakes 25min, Magneto separate goes out modified Nanometer Magnetite, after absolute ethanol washing 2 times, is transferred to there-necked flask, add 20mL deionized water again, be water base Fe 3o 4suspension;
(2) to Fe 3o 4add 0.2225g polyethylene glycol in suspension, dissolve; When bath temperature 59 DEG C, mixing speed 1200rpm, drip 50mL0.4mol/L ZrOCl with 7mL/min 2solution, then drip at a slow speed 2mol/L ammonia spirit with 2mL/min, until stop dripping when pH remains 9; Leave standstill aging 30min, obtain sol precipitation, Magneto separate goes out solid product, with deionized water cyclic washing until pH is neutral, and can't detect Cl -, last suction filtration obtains filter cake;
(3) in filter cake, inject 240mL n-butanol, after mixing making beating evenly, carry out azeotropic distillation.After end to be distilled, in 120 DEG C of vacuum drying 12h, take out grinding, cross 200 mesh sieves, obtain fluorine ion absorber magnetic Nano zirconium hydroxide.
ZrOCl when the present embodiment prepares magnetic Nano zirconium hydroxide 2and Fe 3o 4mol ratio is 3:1.
Embodiment three:
The preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion of the present invention, concrete steps are as follows:
(1) 1g Fe is taken 3o 4nano particle, joins ultrasonic wave dispersion 25min in 60mL0.25mol/L sodium citrate solution, then shakes 20min, Magneto separate goes out modified Nanometer Magnetite, after absolute ethanol washing 2 times, is transferred to there-necked flask, add 20mL deionized water again, be water base Fe 3o 4suspension;
(2) to Fe 3o 4add 0.1335g polyethylene glycol in suspension, dissolve; When bath temperature 61 DEG C, mixing speed 1000rpm, drip 50mL0.5mol/LZrOCl with 8mL/min 2solution, then drip at a slow speed 1.5mol/L ammonia spirit with 3mL/min, until stop dripping when pH remains 10; Leave standstill aging 30min, obtain sol precipitation, Magneto separate goes out solid product, with deionized water cyclic washing until pH is neutral, and can't detect Cl -, last suction filtration obtains filter cake;
(3) in filter cake, inject 300mL n-butanol, after mixing making beating evenly, carry out azeotropic distillation.After end to be distilled, in 120 DEG C of vacuum drying 12h, take out grinding, cross 200 mesh sieves, obtain fluorine ion absorber magnetic Nano zirconium hydroxide.
ZrOCl when the present embodiment prepares magnetic Nano zirconium hydroxide 2and Fe 3o 4mol ratio is 8:1.

Claims (5)

1., for a preparation method for the magnetic zirconium hydroxide adsorbent of Adsorption of fluoride ion, it comprises the steps:
(1) be 1g:(50 ~ 80 according to the ratio of ferriferrous oxide nano-particle and sodium citrate solution) mL, nano ferriferrous oxide being joined concentration is in the sodium citrate solution of 0.2 ~ 0.25mol/L, first ultrasonic wave dispersion 20 ~ 30min, constant-temperature table concussion 20 ~ 30min again, Magneto separate goes out modified magnetic ferroferric oxide nano-particles;
(2) by modified magnetic ferroferric oxide nano-particles absolute ethanol washing, be then transferred in container, add deionized water, obtain water base Fe 3o 4suspension;
(3) to water base Fe 3o 4add polyethylene glycol in suspension to dissolve; Then, under the condition of bath temperature 59 ~ 61 DEG C, mixing speed 900 ~ 1200rpm, fast drop concentration is the ZrOCl of 0.4 ~ 0.5mol/L 2solution, ZrOCl 2the addition of solution is ZrOCl 2and Fe 3o 4mol ratio is 3 ~ 11:1; Drip at a slow speed the ammonia spirit that concentration is 1.5 ~ 2mol/L again until stop when pH is 9 ~ 10 dripping; Leave standstill aging 30min, obtain sol precipitation, Magneto separate goes out solid product, with deionized water cyclic washing until pH is neutral and can't detect Cl -, last suction filtration obtains filter cake;
(4) in filter cake, the n-butanol of 8 ~ 10 times of volumes is injected, after mixing making beating evenly, by the ZrO (OH) obtained 2/ Fe 3o 4wet colloidal sol carries out azeotropic distillation to remove moisture; End final vacuum to be distilled is dry, and after taking out, grinding is sieved, and obtains fluorine ion absorber magnetic zirconium hydroxide.
2. the preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion according to claim 1, it is characterized in that: in described step (1), be 1g:60mL according to the ratio of ferriferrous oxide nano-particle and sodium citrate solution, nano ferriferrous oxide being joined concentration is in the sodium citrate solution of 0.25mol/L, ultrasonic dispersing time is 25min, and the constant-temperature table concussion time is 25min.
3. the preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion according to claim 1, is characterized in that: in described step (3), and the quality of the polyethylene glycol of interpolation is ZrOCl 23 ~ 6% of quality; The ZrOCl of fast drop 0.5mol/L 2solution, rate of addition is 7 ~ 9mL/min; Drip at a slow speed the ammonia spirit of 2mol/L, rate of addition is 2 ~ 3mL/min.
4. the preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion according to claim 1, is characterized in that: in described step (3), to water base Fe 3o 4add polyethylene glycol in suspension to dissolve; Bath temperature is 60 DEG C, mixing speed is 1000rpm, ZrOCl 2the addition of solution is ZrOCl 2and Fe 3o 4mol ratio is 8:1.
5. the preparation method of the magnetic zirconium hydroxide adsorbent for Adsorption of fluoride ion according to claim 1, is characterized in that: in described step (4), injects the n-butanol of 10 times of volumes in filter cake.
CN201410534792.0A 2014-10-10 2014-10-10 Preparation method of magnetic zirconium hydroxide adsorbent for absorbing fluorine ions Pending CN104275145A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110102265A (en) * 2019-04-04 2019-08-09 浙江树人学院（浙江树人大学） For the load zirconium biology compound adsorbent and regeneration method of removing fluor in water and application
CN111439782A (en) * 2020-03-04 2020-07-24 山西新华化工有限责任公司 Synchronous protection NH3/SO2Preparation method of zirconium hydroxide protective material

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CN101445277A (en) * 2008-11-14 2009-06-03 东北大学 Nano-crystalline Fe*O* particles with high absorption capacity and preparation method thereof
CN102258978A (en) * 2011-06-24 2011-11-30 淮阴师范学院 Method for preparing nano Fe3O4 coated attapulgite magnetic composite adsorbent
CN102872790A (en) * 2012-09-24 2013-01-16 中国地质大学（武汉） Sulfate radical sorbent magnetic nanometer zirconium hydroxide and preparation method thereof
CN102941064A (en) * 2012-12-12 2013-02-27 南京大学 Zirconium oxide modified active carbon fiber and application of zirconium oxide modified active carbon fiber for removing phosphates from water body

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JPH06154767A (en) * 1992-11-27 1994-06-03 Fuji Kasui Kogyo Kk Method for treating fluorine-containing drain
CN101445277A (en) * 2008-11-14 2009-06-03 东北大学 Nano-crystalline Fe*O* particles with high absorption capacity and preparation method thereof
CN102258978A (en) * 2011-06-24 2011-11-30 淮阴师范学院 Method for preparing nano Fe3O4 coated attapulgite magnetic composite adsorbent
CN102872790A (en) * 2012-09-24 2013-01-16 中国地质大学（武汉） Sulfate radical sorbent magnetic nanometer zirconium hydroxide and preparation method thereof
CN102941064A (en) * 2012-12-12 2013-02-27 南京大学 Zirconium oxide modified active carbon fiber and application of zirconium oxide modified active carbon fiber for removing phosphates from water body

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* Cited by examiner, † Cited by third party
Title
季建文: "《铀矿山废水处理》", 31 March 1982 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110102265A (en) * 2019-04-04 2019-08-09 浙江树人学院（浙江树人大学） For the load zirconium biology compound adsorbent and regeneration method of removing fluor in water and application
CN111439782A (en) * 2020-03-04 2020-07-24 山西新华化工有限责任公司 Synchronous protection NH3/SO2Preparation method of zirconium hydroxide protective material
CN111439782B (en) * 2020-03-04 2022-07-29 山西新华防化装备研究院有限公司 Synchronous protection NH 3 /SO 2 Preparation method of zirconium hydroxide protective material

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