CN102600794A - Two preparation methods of nanometer magnetic adsorbent - Google Patents
Two preparation methods of nanometer magnetic adsorbent Download PDFInfo
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- CN102600794A CN102600794A CN2012101019167A CN201210101916A CN102600794A CN 102600794 A CN102600794 A CN 102600794A CN 2012101019167 A CN2012101019167 A CN 2012101019167A CN 201210101916 A CN201210101916 A CN 201210101916A CN 102600794 A CN102600794 A CN 102600794A
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Abstract
The invention relates to two preparation methods of nanometer magnetic adsorbents. The obtained nanometer magnetic adsorbents are used for the treatment of heavy-metal ion sewage and comprise nanometer magnetic core clad nanometer silicon dioxide and nanometer magnetic adsorbent surface bonded nanometer magnetic particles. The adsorbents prepared by adopting the two methods have magnetism. By using the nanometer magnetic adsorbents, the adsorption efficiency can be improved, the separation efficiency of the adsorbents is improved by adopting a magnetic separation technique and secondary pollution is avoided. The adsorbents can be regenerated and reused and the recovery of heavy metals can be realized.
Description
Technical field
The present invention relates to absorption method and handle the heavy metal polluted waste water field, be specifically related to the method for the preparation of two kinds of magnetic adsorbents, with and containing the application of effluent containing heavy metal ions in handling.
Background technology
The heavy-metal pollution water system has become one of serious environmental problem in the world today.At present, this type of method of wastewater treatment roughly is divided into three major types: (1) chemical method mainly comprises neutralization precipitation method, sulphide precipitation, the ferrite precipitation method, oxidation-reduction method, electrochemical process and macromolecule method; (2) physics method: mainly comprise absorption method, extraction, ion-exchange, membrane separation process, evaporation and freezing method; (3) biological treatment mainly comprises bio-flocculation process, biochemical process and phytoremediation method.In these methods, the precipitation method, oxidation-reduction method and macromolecule method often consume a large amount of chemical agents and also produce secondary pollution simultaneously; Electrochemical process can consume a large amount of electric energy; Extraction, ion-exchange, membrane separation process and evaporation coagulation rule equipment drop into more, have problems such as processing cost is higher; Imperfection is gone back in the development of biological treatment.Absorption method since advantage such as applicable system is many, secondary pollution is little and cost is lower in wastewater treatment, be applied.
Restriction absorption method main cause of extensive use in heavy metal containing wastewater treatment is that adsorbents adsorb efficient is lower.Along with the development of nanometer technology, nano level adsorbent is because big specific area can improve adsorption efficiency greatly.But along with reducing of grain graininess, on separating, brought the problem that separative efficiency reduces and cost improves again, restricted the development of nano adsorber in this field.
Nano adsorber combines the nano-magnetic compound adsorbent that forms with nano magnetic material, but not only utilizes the characteristics of its Magnetic Isolation to remedy the deficiency of simple nano adsorber, also can under the effect in magnetic field, strengthen stirring, the raising adsorption efficiency.
Summary of the invention
The present situation of and difficult separation low to adsorbents adsorb efficient the invention provides two kinds of magnetic Nano preparation of adsorbent methods.
The preparation method of silicon oxide coating nano ferronickel nano-magnetic compound adsorbent of the present invention is following:
Compound concentration is less than 2% ferronickel mixed solution, and wherein nickel shared mass ratio in mixture is 0～100%.Using mass percent concentration is pH value to 4.5～11.0 that 1～20% sodium hydroxide solution is regulated mixed liquor; Add complexant and surfactant that quality is a ferronickel gross mass 20～200% respectively; And to add quality be the reducing agent of ferronickel gross mass 100～2000%, fully mixing under nitrogen protection.This mixed solution is transferred in the hydrothermal reaction kettle, reacts 1～19h down at 120～210 ℃.Reaction system naturally cools to room temperature.Method with magnetic separates is separated the magnetic-particle that makes.With the gained magnetic-particle repeatedly with the clear water washing.
The magnetic-particle that obtains after the washing is placed the sodium silicate solution of quality percentage composition 0.01～20%, feed gas while stirring, CO in the gas
2Content is 20%～100%, and all the other are nitrogen.Gas flow is controlled at 30～120ml/min, drops to 9 until the pH of sodium silicate solution value.Continue to leave standstill behind the strong agitation 30min, separate the magnetic composite particles that makes with the method that magnetic separates.The magnetic composite particles that separation is obtained washs with clear water, obtains the magnetic compound adsorbent of coated with silica ferronickel magnetic core.
Be dissolved in the sodium chloride solution after the method that the renovation process of magnetic compound adsorbent separates with magnetic for the adsorbent that will adsorb heavy metal ion among the present invention is separated, under ultrasonic or powerful stirring condition, isolate the heavy metal ion that is adsorbed on adsorbent surface.Separate through magnetic, the magnetic composite nano sorbent circulation is used, and adopts the method for extract and separate from sodium chloride solution, to reclaim heavy metal ion, and sodium chloride solution is used further to the activation of adsorbent.
The preparation method of the magnetic compound adsorbent of the present invention surface combination magnetic nanoparticle is following:
Compound concentration is less than 2% ferronickel mixed solution, and wherein nickel shared mass ratio in mixture is 0～100%.In CNT or active carbon or this solution of new system nano silicon dispersion.Using mass percent concentration is pH value to 4.5～11.0 that 1～20% sodium hydroxide solution is regulated mixed liquor; Add complexant and surfactant that quality is a ferronickel gross mass 20～200% respectively; And to add quality be the reducing agent of ferronickel gross mass 100～2000%, fully mixing under nitrogen protection.This mixed solution is transferred in the hydrothermal reaction kettle, reacts 1～19h down at 120～210 ℃.Reaction system naturally cools to room temperature.Method with magnetic separates is separated the magnetic composite particles that makes.Through repeatedly washing, the surface combines the magnetic compound adsorbent of magnetic nanoparticle.
The renovation process of magnetic compound adsorbent fully stirs separation of heavy metal ions and adsorbent for the adsorbent that will the adsorb heavy metal ion character according to heavy metal ion is dissolved in it in weak acid or the weakly alkaline solution among the present invention.If employing acid solution; Then the ferronickel as magnetic-particle can be dissolved in acid solution, and adsorbent needs isolated by filtration, and filtrating is reclaimed heavy metal ion with method of extraction; After ferronickel ion in the raffinate is regulated the pH value, multiplexing in the magnetic composite nano preparation of adsorbent with the filter residue counterpoise; If the employing weakly alkaline solution then can be with magnetism separate method directly with receiving adsorbent.
Preparation ferronickel mixed solution can use soluble nickel salt and molysite to comprise nickel chloride, nickelous sulfate, nickel nitrate, nickel acetate in two kinds of methods, ferrous sulfate, sulfate iron ammonium, frerrous chloride, ferrous sulfate, ferrous nitrate; Also can adopt metallic nickel and metallic iron, in acid solution, mixed solution processed in its dissolving.The complexant that uses comprises natrium citricum, sodium tartrate, glucose, sucrose, EDTA; The reducing agent that uses comprises hydrazine hydrate, sodium borohydride, sodium hypophosphite; Surfactant comprises polyethylene glycol, dodecyl sodium sulfate.
Advantage of the present invention is that (1) magnetic composite nano preparation of adsorbent method is simple, the adsorption efficiency height; (2) adsorbent is reusable, and (3) because adopt Magnetic Isolation, separation is an easy operating; High efficiency is arranged again; Can not cause secondary pollution, the heavy metal ion that (4) are adsorbed also can be recycled, and has avoided the waste of resource.
The specific embodiment
Embodiment 1
Be dissolved in 100ml water with the nickel chloride of 0.5g and 0.5g ferrous sulfate and be mixed with the ferronickel mixed solution; Using mass percent concentration is the pH value to 5.5 that 1% sodium hydroxide solution is regulated mixed liquor; The adding quality is respectively natrium citricum and the polyethylene glycol of 0.2g, stirs.Drip the 3g hydrazine hydrate, under nitrogen protection, fully mix.This mixed solution is transferred in the hydrothermal reaction kettle, reacts 2h down at 120 ℃.Reaction system naturally cools to room temperature.Method with magnetic separates is separated the magnetic-particle that makes.The magnetic-particle that separation is obtained washs repeatedly with clear water, and the method for all separating with magnetic is isolated magnetic-particle.
The magnetic-particle that obtains after the washing is placed the sodium silicate solution of quality percentage composition 1%, feed gas while stirring, CO in the gas
2Content 20%, all the other are nitrogen.Gas flow is controlled at 30ml/min, drops to 9 until the pH of sodium silicate solution value.Continue to leave standstill behind the strong agitation 30min, separate the magnetic composite particles that makes with the method that magnetic separates.The magnetic composite particles that separation is obtained washs with clear water, obtains the magnetic compound adsorbent of coated with silica ferronickel magnetic core.
Is in the copper-bath of 13ppm with the magnetic compound adsorbent that obtains in initial concentration, fully stirs, and with the method that magnetic separates the magnetic compound adsorbent is separated.Copper ion concentration is 0.19ppm in the mensuration ortho-sulfuric acid copper solution.
The compound adsorbent that has adsorbed copper ion is dissolved in the saturated nacl aqueous solution ultrasonic agitation.Separate through magnetic, the magnetic composite nano sorbent circulation is used again, and adopts the method for extract and separate from sodium chloride solution, to reclaim copper metal ion, and sodium chloride solution is used for the activation of adsorbent.
Embodiment 2
Take by weighing 0.2g iron powder and 0.7g nickel powder, it is dissolved in the hydrochloric acid of 10ml 1mol/L, solution is diluted to 100ml.The CNT that takes by weighing 1g is scattered in it in this solution.Using mass percent concentration is the pH value to 9.0 that 1% sodium hydroxide solution is regulated mixed liquor, and adding quality is the sodium tartrate of 0.5g and the dodecyl sodium sulfate of 0.4g, abundant mixing under nitrogen protection, dropping 4g hydrazine hydrate.This mixed solution is transferred in the hydrothermal reaction kettle, at 160 ℃ of reaction 1h.Reaction system naturally cools to room temperature.Method with magnetic separates is separated the magnetic composite particles that makes.The magnetic composite particles that separation is obtained washs with clear water, obtains the magnetic compound adsorbent that the nano adsorber surface combines magnetic-particle.
Is in the ammonium molybdate solution of 50ppm with the magnetic compound adsorbent that obtains in initial concentration, fully stirs, and with the method that magnetic separates the magnetic compound adsorbent is separated.Molybdenum ion concentration is 1.0ppm in the mensuration ortho-sulfuric acid copper solution.
The compound adsorbent that has adsorbed molybdenum ion is dissolved in the weak ammonia solution, fully stirs.Magnetic Isolation, the molybdenum in the solution is recycled, and magnetic adsorbent recycles.
Claims (5)
1. the preparation method of silicon oxide coating nano ferronickel nano-magnetic compound adsorbent is characterized in that may further comprise the steps:
(1) preparation ferronickel mixed solution, the pH value with sodium hydroxide solution is regulated mixed liquor adds complexant and surfactant in solution, under nitrogen protection, fully mix, and adds reducing agent.This mixed solution is transferred in the hydrothermal reaction kettle, reacts 1～19h down at 120～210 ℃.Reaction system naturally cools to room temperature.Method with magnetic separates is separated the magnetic-particle that makes.
(2) magnetic-particle that obtains after will washing places the sodium silicate solution of quality percentage composition 0.01～20%, feeds CO while stirring
2Gas drops to 9 until the pH of sodium silicate solution value.Leave standstill, separate the magnetic composite particles that makes with the method that magnetic separates.
2. the surface combines the preparation method of the magnetic compound adsorbent of magnetic nanoparticle, it is characterized in that may further comprise the steps:
Preparation ferronickel mixed solution is in CNT or active carbon or this solution of new system nano silicon dispersion.PH value with sodium hydroxide solution is regulated mixed liquor adds complexant and surfactant in solution, under nitrogen protection, fully mix, and adds reducing agent.This mixed solution is transferred in the hydrothermal reaction kettle, reacts 1～19h down at 120～210 ℃.Reaction system naturally cools to room temperature.Method with magnetic separates is separated the magnetic-particle that makes.
3. according to claim 1, the preparation method of 2 described preparation nano-compound adsorbents is characterized in that: described compound concentration is less than 2% ferronickel mixed solution, and wherein nickel shared mass ratio in mixture is 0～100%; Used sodium hydroxide solution mass percent concentration is 1～20%; The pH value of mixed liquor is adjusted to 4.5～11.0; Complexant and amount of surfactant are ferronickel gross mass 20～200%, and the reducing agent consumption is the reducing agent of ferronickel gross mass 100～2000%.
4. according to claim 1; The preparation method of 2 described preparation nano-compound adsorbents; It is characterized in that: the ferronickel mixed solution can use soluble nickel salt and molysite to comprise nickel chloride, nickelous sulfate, nickel nitrate, nickel acetate; Ferrous sulfate, sulfate iron ammonium, frerrous chloride, ferrous sulfate, ferrous nitrate; Also can adopt metallic nickel and metallic iron, in acid solution, mixed solution processed in its dissolving; Complexant comprises natrium citricum, sodium tartrate, glucose, sucrose, EDTA; The reducing agent that uses comprises hydrazine hydrate, sodium borohydride, sodium hypophosphite; Surfactant comprises polyethylene glycol, dodecyl sodium sulfate.
5. according to claim 1, the application of 2 described preparation nano-compound adsorbents: it is characterized in that the heavy metal ion in the adsorbed water.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263890A (en) * | 2013-05-24 | 2013-08-28 | 中国计量学院 | Magnetic bamboo charcoal material and preparation method thereof |
| CN105170084A (en) * | 2015-09-17 | 2015-12-23 | 上海应用技术学院 | Preparation method of magnetic active carbon for adsorbing heavy metals in water |
| CN103721689B (en) * | 2014-01-08 | 2016-01-13 | 湖南大学 | Magnetic mesoporous silicon, preparation method and magnetic mesoporous silicon adsorbent, preparation method and application |
| CN105671522A (en) * | 2016-01-20 | 2016-06-15 | 东北大学 | Method for coating amorphous silicon dioxide membranes on surfaces of solid particles |
| CN108017219A (en) * | 2017-12-12 | 2018-05-11 | 北京理工水环境科学研究院有限公司 | A kind of high-fluorine water processing equipment |
| CN110102262A (en) * | 2019-06-21 | 2019-08-09 | 苏州科技大学 | A kind of magnetic active carbon composite material and its preparation method and application |
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| CN101311281A (en) * | 2007-05-24 | 2008-11-26 | 东北大学 | Green metallurgical process for integrated utilization of nickel laterite ore |
| CN101658933A (en) * | 2009-09-21 | 2010-03-03 | 安徽师范大学 | Preparation method of magnetic nano-materials and application thereof |
| CN102350313A (en) * | 2011-08-30 | 2012-02-15 | 郑州航空工业管理学院 | Preparation method and application of copper and ferrous magnetic metal oxide modified fly ash phosphorus adsorbent |
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| US4382982A (en) * | 1979-12-07 | 1983-05-10 | Ici Australia Limited | Process for protecting magnetic particles with chromium oxide |
| CN101090018A (en) * | 2007-04-30 | 2007-12-19 | 吉林大学 | Silica-magnetic composite micropartical and its preparation method |
| CN101311281A (en) * | 2007-05-24 | 2008-11-26 | 东北大学 | Green metallurgical process for integrated utilization of nickel laterite ore |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263890A (en) * | 2013-05-24 | 2013-08-28 | 中国计量学院 | Magnetic bamboo charcoal material and preparation method thereof |
| CN103721689B (en) * | 2014-01-08 | 2016-01-13 | 湖南大学 | Magnetic mesoporous silicon, preparation method and magnetic mesoporous silicon adsorbent, preparation method and application |
| CN105170084A (en) * | 2015-09-17 | 2015-12-23 | 上海应用技术学院 | Preparation method of magnetic active carbon for adsorbing heavy metals in water |
| CN105671522A (en) * | 2016-01-20 | 2016-06-15 | 东北大学 | Method for coating amorphous silicon dioxide membranes on surfaces of solid particles |
| CN108017219A (en) * | 2017-12-12 | 2018-05-11 | 北京理工水环境科学研究院有限公司 | A kind of high-fluorine water processing equipment |
| CN108017219B (en) * | 2017-12-12 | 2021-01-05 | 北京理工水环境科学研究院有限公司 | High fluorine water treatment facilities |
| CN110102262A (en) * | 2019-06-21 | 2019-08-09 | 苏州科技大学 | A kind of magnetic active carbon composite material and its preparation method and application |
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Application publication date: 20120725 |