CN104971688B - A kind of preparation method of nano magnetic particle adsorbent - Google Patents
A kind of preparation method of nano magnetic particle adsorbent Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of nano magnetic particle adsorbent, it is characterised in that comprises the following steps：(1) weigh trivalent iron salt, divalent iron salt and tetravalence zirconates to be placed in container, be dissolved in water obtained mixed aqueous solution；(2) under mechanical agitation, alkali lye is added dropwise in mixed aqueous solution made from step (1), the mixed liquor that pH value is 6.5~8.5 is made；(3) after completion of dropwise addition, mixed liquor is aged 10~20h at 45~75 DEG C, obtains being aged sample；(4) it will be aged after sample clean dry, that is, obtain purpose product adsorbent.Compared with prior art, the present invention has the advantages that cost is low, adsorbent absorption property is excellent, recyclable, technological process is simple.
Description
Technical field
The present invention relates to a kind of preparation of adsorbent, it is used to remove anionic pollutant in sewage more particularly, to a kind of
The preparation of nano magnetic particle adsorbent.
Background technology
In recent years, China faces the water resource and water environmental problems of sternness.On the one hand, China's water storage and conservation is less, people
The equal water resource volume of holding is 2300m3, only the 1/4 of world average level.On the other hand, water pollution problems is serious in recent years, plus
The acute scarcity of water resource.In numerous pollutants, anionic pollutant occupies larger ratio, and generates suitable journey
The harm of degree.In water body common anionic pollutant include using phosphate, arsenate, fluorine ion as representative inorganic anion
Pollutant, and the organic anion pollutant by representative of humic acid.Wherein, phosphate is raw from sanitary sewage, industry
Production and agricultural area source, are most commonly seen anionic pollutants, it is considered to be the multiple large-size lake water bodys of China are rich in recent years
The basic reason broken out in nutrient laden problem set；Arsenate pollutes, and is primarily generated at the arsenic such as Guangxi, Hunan, Guizhou rich in mineral resources
In the Mining Development in area and associated production technological process, with extremely strong toxicity, the first kind is classified as by WHO
Carcinogenic substance；Fluorine ion typically results from mining industry or Ferrous Metallurgy production, and the exceeded underground water of fluorine ion is used as drinking water source meeting
Trigger the diseases such as fluorosis of bone, mottled teeth, current China still there are 70,000,000 people drinking high-fluorine water；During humic acid is natural water body
Main organic components, are final product of the animals and plants remnant Jing Guo various degradations, if by drinking water treatment chlorination stream
Journey, then can produce the various halide with " three cause " effect, therefore turn into the pollutant drunk and be primarily upon in water pretreatment.
The removal of anionic pollutant in water, common method has bioanalysis, membrane filter method, chemical precipitation method etc..However,
Foregoing several method is extremely limited for the anionic pollutant removal effect of low concentration, it is impossible to meet increasingly strict water environment
Quality standard.And absorption method, then with the removal suitable for low concentration pollutant, production sludge quantity it is few, cost is low, treatment effect is steady
The advantages of determining, can effectively solve the problem of removal of common process anionic pollutant can not be up to standard.It has now been developed
Diversified anion adsorbent and its application method for water process.
Zirconium as a kind of transition metal, for the anion such as phosphate radical, arsenate, fluorine ion and humic acid have compared with
Good affinity and selectivity.Content of the zr element in the earth's crust be 130mg/kg, the metallic element common higher than copper, zinc etc.,
Therefore with being relatively easy to obtain the characteristics of.In addition, zirconium content in human body is 250mg, thus also there is biological safety.It is based on
Above reason, zirconium oxide and zirconium base adsorbent have been widely used in water treatment field.China Patent Publication No.
CN101555078A discloses a kind of method of use nano zircite fluorine removal, and fluoride waste is passed through and filled out with nano zircite particle
Water outlet 1mg/L under filtering absorption, water inlet 10mg/L, flow velocity 9BV/h is carried out in the reaction tower of dress, discharge standard has been reached.However,
Nano zircite is minimum due to particle, and strainability is poor, and it handles the less efficient of sewage, it is impossible to meet wanting for large-scale promotion
Ask.If it directly mixed with sewage, efficiency can be raised significantly, can not but solve the regeneration issues after adsorption saturation.Perhaps
Many researchers give solution to this, i.e., zirconia particles are carried on a series of matrix, so as to improve its filtering
Performance simultaneously ensures recovery of the adsorbent after adsorption saturation.For example China Patent Publication No. CN102942239A discloses a kind of use
In the polymer matrix compound adsorbent of fluorine removal, unformed zirconium oxide is supported on to the hole of styrene-divinylbenzene sphere polymers
In hole.The adsorbent produces preenrichment for fluorine ion by polymer and acted on, and fluorine ion is diffused in hole and by diffusion
Effect is fixed on hole inwall, occurs obligate absorption on nano zircite particle surface afterwards.The adsorbent of adsorption saturation is used
NaOH-NaCl mixed liquors are regenerated.This method can improve the hydrodynamics of zirconium oxide well, and then promote its mistake
Filter performance.Meanwhile, load is it is also possible that the reference area expansion of zirconium oxide, promotes it further to play a role.But, it is in office
The amount of loaded zirconia is limited on what matrix.Excessive load may block the hole of dimer, influence it to filter
Performance.Therefore, matrix loaded zirconia is used, as this thinking of filtrate of purification anion contamination, in adsorption capacity
Still there is limitation.
For the limitation of filtration method, it may be considered that in the making that magnetic separation technique is introduced into zirconium base adsorbent.The magnetic being made
Property the relative particle as filtrate or modification of filtration medium adsorbent of particle, specific surface area big the features such as small with particle size, thus
Be conducive to absorption.Absorption can carry out separation of solid and liquid, the problem of also solving recovery after terminating by externally-applied magnetic field.Existing magnetic
Property adsorbent, be usually magnetic nanoparticle (such as Fe that will make3O4) use SiO2It is coated with, then utilizes SiO2Surface
Abundant point position is further modified, the need for being adapted to the pollutant to be adsorbed.China Patent Publication No.
CN104148008A discloses a kind of preparation method of the magnetic adsorbent adsorbed for lead ion.The technology is being coated with oxidation
The magnetic iron ore surface of silicon has been coated with one layer of titanium phosphate again, in favor of the suction-operated of lead ion.Similar, China Patent Publication No.
CN103065754A, which is disclosed, a kind of is being coated with the magnetic iron ore pan coating benzene sulfonic acid of silica, the suction to adsorb antibiotic
Attached dose.Both the above adsorbent have received more satisfied effect.The above method has problems in that, the making of adsorbent
It is minimum to need three steps, complex operation；Silane TEOS is often used when being coated with silica simultaneously, it has inflammability and to human body
Toxicity so that there may be secondary pollution for such technique.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is used to remove sewage
The preparation of the nano magnetic particle adsorbent of middle anionic pollutant.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of nano magnetic particle adsorbent, comprises the following steps：
(1) weigh trivalent iron salt, divalent iron salt and tetravalence zirconates to be placed in container, be dissolved in water obtained mixed aqueous solution；
(2) compound concentration is 1.2~6mol/L alkali lye, under mechanical agitation, and alkali lye is added dropwise into step (1) system
In the mixed aqueous solution obtained, the mixed liquor that pH value is 6.5~8.5 is made；
(3) after completion of dropwise addition, mixed liquor is aged 10~20h at 45~75 DEG C, promotes it to be self-assembly of and obtains
The ageing sample of " shell-core " structure, wherein, magnetic iron ore is core, and zirconium oxide is shell, and core is used for Magneto separate, and shell, which is used to adsorb, to be polluted
Thing；
(4) it will be aged after sample clean dry, that is, obtain purpose product adsorbent.
Described trivalent iron salt is iron chloride；Described divalent iron salt is ferrous sulfate；Described tetravalence zirconates is chlorine oxygen
Change zirconium or nitric acid oxidation zirconium.
In mixed aqueous solution described in step (1), ferric iron and ferrous atomic molar ratio are 2:1, the original of iron and zirconium
Sub- mol ratio is 6~2:1.
Alkali lye described in step (2) is NaOH solution, and its concentration is 1.2~6mol/L.
Churned mechanically rotating speed is 200~500rpm in step (2), and the rate of addition of alkali lye is 0.05~5ml/min.
The drying mode of ageing sample is drying, is dried in vacuo or lyophilized in step (4).
Adsorbent produced by the present invention can be desorbed by certain method after adsorption saturation, realize anionic pollutant
Recycling, the sample of sorbent after desorption can recycle through regeneration, the method tool of adsorbent desorption and regeneration of the invention
Body is as follows：
(a) adsorbent of adsorption saturation is mixed with 0.5~3mol/L alkali lye, the solid-to-liquid ratio of adsorbent and alkali lye is 1
~5g/L, is then desorbed, and desorption time is 4~10h, after the completion of desorption, the sample of sorbent that separation of solid and liquid is desorbed；
(b) adsorbent after desorption is mixed with water, obtains mixed liquor, H is added dropwise+Concentration is 0.01~1mol/L acid solution
Mixed liquor is recalled to certain pH value, the pH value is pH of the adsorbent when absorption is mixed before with equivalent water；
(c) by mixed liquor separation of solid and liquid, after solid is cleaned up with water, you can used into next round.
Nano magnetic particle adsorbent produced by the present invention have fairly good magnetic (>20emu/g), it is possible to achieve absorption
Later the quick Magneto separate of adsorbent and recovery.Saturated extent of adsorption to adsorbent is more than 1mmol/g, to the moon of low concentration
Ionic contamination has lasting purification function, using repeatedly after still water outlet still can be with up to standard.By by titration end-point control
System is more than 6.5, it is ensured that the formation of the magnetite cores with good crystal formation；Unformed hydrous zirconium oxide(HZO) is relative due to structure
Loosely, the outside of magnetic iron ore nucleus is wrapped in, " shell-core " structure has been self-assembly of, this structure is very beneficial for energy of adsorption
The stronger zirconium oxide of power plays a role in adsorbent surface, while ensure the magnetic of adsorbent in itself, and according to Anion-adsorption
Characteristic, if alkalescence is presented in the too high surface that can make magnetic oxygenated zirconium of titration end-point during synthesis sorbing material, be unfavorable for it is cloudy from
The absorption of son, therefore the upper limit of titration end-point is defined as 8.5.During synthesizing magnetic granule adsorbent, by Fe atoms and Zr atoms
Mol ratio is controlled 6~2:1, it is ensured that the magnetic and absorption property of magnetic-particle sorbent material, both will not be because of magnetic iron ore
Ratio it is too low cause material magnetic be difficult to ensure that, again will not because of zirconium oxide ratio it is too low so that material surface can not be complete
Zirconium coating is oxidized, its adsorption capacity is influenceed.
Compared with prior art, the present invention has advantages below：
1) cost is low：Zirconates, molysite and sodium hydroxide used in the present invention it is cheap, preparation method condition is easy to control
System；
2) absorption property is excellent, recyclable：The magnetic nano zircite adsorbent of tool produced by the present invention, both make use of
The strong adsorption capacity of zirconium oxide, realizes the removal to a variety of anionic pollutants, while ensureing by the magnetic iron ore in adsorbent
Its reclaiming；
3) technological process is simple：" shell-core " structure obtained by traditional three-step approach is obtained by one-step method so that magnetic oxygen
Changing in zirconium, there is stronger adsorption capacity zirconium oxide to be partially located in sorbent particle surfaces, and magnetic iron ore part is located at adsorbent
Intragranular portion, obtains easily separated, efficient with simple method, repeatedly used adsorbent after saturation；
4) it is pollution-free：Any organic solvent and toxic reagent are not needed in preparation process, with environment friendly；
5) adsorbent can be desorbed after adsorption saturation by certain method, realize that the recycling of anionic pollutant is returned
Receive.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Fig. 2 is the transmission electron microscope picture of obtained adsorbent in embodiments of the invention 1.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1
As shown in figure 1, by 0.5mol FeSO4·7H2O、1mol FeCl3·6H2O and 0.4mol ZrOCl2·8H2O,
It is made into 500ml mixed aqueous solutions.Mechanical agitation is applied to the aqueous solution with 400 revs/min of speed, 6mol/L is then added dropwise
NaOH solution is stirred for half an hour, then the mixed aqueous solution is aged at 60 DEG C to mixed aqueous solution pH=7.6 after adding
12h, carries out separation of solid and liquid using magnetic separation technique to mixed liquor separation 10min afterwards, will obtain after solid portion cleans with water,
Dry, that is, obtain purpose product adsorbent.
Transmission electron microscope (TEM) scanning is carried out to obtained adsorbent, it is found that adsorbent forms unformed aqua oxidation
Zirconium is wrapped in " shell-core " structure in the outside of magnetic iron ore nucleus, as shown in Figure 2.
Shanghai sewage plant secondary biochemical treatment tail water dephosphorization is carried out using above-mentioned adsorbent, as a result shown：
(1) adsorbent is 42mg/g to phosphatic maximal absorptive capacity；
(2) saturation magnetization of adsorbent is 25emu/g, and quick Magneto separate can be realized by magnetic field；
(3) 0.5h reaction time is ensured, 1kg/ tons of dosage (uses Shanghai area running water in 2mg P/L sewage
Configuration) in, run 7 times, water outlet phosphorus concentration is respectively less than 0.5mg/L, meet country in town sewage plant secondary effluent draining
One-level A standards on phosphorus；
(4) adsorbent of adsorption saturation, after being desorbed and regenerated with 1mol/L NaOH solution, saturated extent of adsorption still has
Remain to maintain this level after original more than 90%, and regeneration repeatedly.
Using above-mentioned adsorbent, Beijing somewhere Fluorine Containing Groundwater is purified.Raw water fluorinated volume is 3.01mg/L, this suction
Attached dose under 1g/L throwing amount, you can to realize more than 90% removal, run multiple stable water outlet national standard 1mg/L with
Under.
Embodiment 2
In adsorbent preparation process, except ZrOCl2·8H2O dosage is that other are same as Example 1 outside 0.6mol.
Saturation magnetization test is carried out to adsorbent obtained above, the saturation magnetization for finding the adsorbent is
23emu/g；The experiment of trivalent arsenate pollutant purification is carried out to adsorbent, maximum adsorption of the adsorbent to trivalent arsenate is found
Measure as 116mg/g.
Purified using this adsorbent Inner Mongol somewhere underground water exceeded to arsenate.The content of arsenic is in raw water
0.33mg/L, main component is trivalent arsenic.Under 1kg/ tons of throwing amount, the aqueous concentration of arsenic is less than 0.05mg/L after 1h reactions,
Meet national standard.Adsorbent water outlet under conditions of running 3 times repeatedly is up to standard all the time.And can continue to make after desorption and regeneration
With.
Embodiment 3
A kind of preparation method of nano magnetic particle adsorbent, its preparation flow comprises the following steps referring to Fig. 1：
(1) respectively by 1molFeSO4·7H2O、2molFeCl3·6H2O and 0.5mol ZrOCl2·8H2O is placed in container
In, be dissolved in water obtained mixed aqueous solution；
(2) compound concentration is 1.2mol/L NaOH solution, in the case where rotating speed is 200rpm mechanical agitation, by NaOH
Solution is added in mixed aqueous solution made from step (1) with 5ml/min rate of addition, and the mixed liquor that pH value is 6.5 is made；
(3) after completion of dropwise addition, mixed liquor is aged 20h at 45 DEG C, promotes it to be self-assembly of and obtains " shell-core " structure
Ageing sample, wherein, magnetic iron ore is core, and zirconium oxide is shell, and core is used for Magneto separate, and shell is used to adsorb pollutant；
(4) ageing sample is separated, is dried after cleaning, that is, obtain purpose product adsorbent.
Embodiment 4
A kind of preparation method of nano magnetic particle adsorbent, comprises the following steps：
(1) respectively by 1molFeSO4·7H2O、2molFeCl3·6H2O and 1.5mol ZrOCl2·8H2O is placed in container
In, be dissolved in water obtained mixed aqueous solution；
(2) compound concentration is 6mol/L NaOH solution, in the case where rotating speed is 500rpm mechanical agitation, NaOH is molten
Liquid is added in mixed aqueous solution made from step (1) with 0.05ml/min rate of addition, and the mixed liquor that pH value is 8.5 is made；
(3) after completion of dropwise addition, mixed liquor is aged 10h at 75 DEG C, promotes it to be self-assembly of and obtains " shell-core " structure
Ageing sample, wherein, magnetic iron ore is core, and zirconium oxide is shell, and core is used for Magneto separate, and shell is used to adsorb pollutant；
(4) ageing sample is separated, is dried in vacuo after cleaning, that is, obtains purpose product adsorbent.
Embodiment 5
A kind of preparation method of nano magnetic particle adsorbent, comprises the following steps：
(1) respectively by 1molFeSO4·7H2O、2molFeCl3·6H2O and 1mol ZrO (NO3)2·H2O is placed in container
In, be dissolved in water obtained mixed aqueous solution；
(2) compound concentration is 3mol/L NaOH solution, in the case where rotating speed is 300rpm mechanical agitation, NaOH is molten
Liquid is added in mixed aqueous solution made from step (1) with 2ml/min rate of addition, and the mixed liquor that pH value is 7.5 is made；
(3) after completion of dropwise addition, mixed liquor is aged 15h at 65 DEG C, promotes it to be self-assembly of and obtains " shell-core " structure
Ageing sample, wherein, magnetic iron ore is core, and zirconium oxide is shell, and core is used for Magneto separate, and shell is used to adsorb pollutant；
(4) ageing sample is separated, is freezed after cleaning, that is, obtain purpose product adsorbent.
Claims (5)
1. a kind of preparation method of nano magnetic particle adsorbent, it is characterised in that comprise the following steps：
(1) weigh trivalent iron salt, divalent iron salt and tetravalence zirconates to be placed in container, be dissolved in water obtained mixed aqueous solution；
(2) under mechanical agitation, alkali lye is added dropwise in mixed aqueous solution made from step (1), be made pH value be 6.5~
8.5 mixed liquor；
(3) after completion of dropwise addition, mixed liquor is aged after 10~20h, separation of solid and liquid at 45~75 DEG C and obtains being aged sample；
(4) it will be aged after sample clean dry, that is, obtain purpose product adsorbent；
In mixed aqueous solution described in step (1), ferric iron and ferrous atomic molar ratio are 2:1, the atom of iron and zirconium rubs
You are than being 6~2:1.
2. a kind of preparation method of nano magnetic particle adsorbent according to claim 1, it is characterised in that described three
Valency molysite is iron chloride；Described divalent iron salt is ferrous sulfate；Described tetravalence zirconates is basic zirconium chloride or nitric acid oxidation zirconium.
3. a kind of preparation method of nano magnetic particle adsorbent according to claim 1, it is characterised in that step (2)
Described in alkali lye be NaOH solution, its concentration be 1.2~6mol/L.
4. a kind of preparation method of nano magnetic particle adsorbent according to claim 1, it is characterised in that step (2)
In churned mechanically rotating speed be 200~500rpm, the rate of addition of alkali lye is 0.05~5ml/min.
5. a kind of preparation method of nano magnetic particle adsorbent according to claim 1, it is characterised in that step (4)
The drying mode of middle ageing sample is drying, vacuum drying or lyophilized.
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| CN105771936A (en) * | 2016-05-13 | 2016-07-20 | 湖南大学 | Magnetic zirconium/iron composite oxide nanometer material, and preparation method and application thereof |
| CN105854783A (en) * | 2016-05-20 | 2016-08-17 | 兰州交通大学 | Instantly regenerated magnetic filter material for removing nitrogen and phosphorus and preparation method of instantly regenerated magnetic filter material |
| CN114590835A (en) * | 2022-02-24 | 2022-06-07 | 清华大学深圳国际研究生院 | Water purification defluorination material based on amorphous zirconia and preparation method thereof |
| CN114984921A (en) * | 2022-06-29 | 2022-09-02 | 成都医学院 | Simple preparation method of magnetic rape straw bio-adsorbent |
| CN117551016B (en) * | 2024-01-11 | 2024-04-05 | 苏州润邦半导体材料科技有限公司 | Method for removing metal ions in organic matters by using magnetic zirconia adsorbent |
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| CN101670267A (en) * | 2009-10-26 | 2010-03-17 | 北京林业大学 | Composite metal oxide de-fluoridation adsorbent and preparation method therefor |
| CN102887819A (en) * | 2011-07-23 | 2013-01-23 | 烟台万华聚氨酯股份有限公司 | Method for preparing 2, 2-dimethylol-1-butanal |
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| CN101670267A (en) * | 2009-10-26 | 2010-03-17 | 北京林业大学 | Composite metal oxide de-fluoridation adsorbent and preparation method therefor |
| CN102887819A (en) * | 2011-07-23 | 2013-01-23 | 烟台万华聚氨酯股份有限公司 | Method for preparing 2, 2-dimethylol-1-butanal |
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