CN104971688A - Preparation method of nanometer magnetic particle adsorbent - Google Patents
Preparation method of nanometer magnetic particle adsorbent Download PDFInfo
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- CN104971688A CN104971688A CN201510435422.6A CN201510435422A CN104971688A CN 104971688 A CN104971688 A CN 104971688A CN 201510435422 A CN201510435422 A CN 201510435422A CN 104971688 A CN104971688 A CN 104971688A
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Abstract
The invention relates to a preparation method of a nanometer magnetic particle adsorbent which is characterized by comprising the following steps: (1) weighing trivalent ferric salt, divalent ferric salt and tetravalent zircon salt, putting into a container, adding water for dissolution to prepare a mixed aqueous solution; (2) dropwise adding alkali liquor into the mixed aqueous solution obtained in the step (1) under mechanical stirring to prepare a mixed solution of which pH value is 6.5-8.5; (3) ageing the mixed solutioin for 10-20h at the temperature of 45-75 DEG C after dripping is ended so as to obtain an aged sample; (4) washing clean and drying the aged sample so as to obtain the target product, the adsorbent. Compared with the prior art, the preparation method has the advantages of low cost, simple technological process and the like; and the prepared adsorbent is excellent in the adsorption performance and is recoverable.
Description
Technical field
The present invention relates to a kind of preparation of adsorbent, especially relating to a kind of preparation of the nano magnetic particle adsorbent for removing anionic pollutant in sewage.
Background technology
In recent years, China faces severe water resource and water environmental problems.On the one hand, China's water storage and conservation is less, and the water resource volume of holding is 2300m per capita
3, be only 1/4 of world average level.On the other hand, water pollution problems is serious in recent years, exacerbates the scarcity of water resource.In numerous pollutants, anionic pollutant occupies larger ratio, and creates the harm of certain degree.The inorganic anion pollutant that it is representative that anionic pollutant common in water body comprises with phosphate, arsenate, fluorine ion, and the organic anion pollutant taking humic acid as representative.Wherein, phosphate sources, in sanitary sewage, industrial production and agricultural area source, is anionic pollutant the most common, is considered to the basic reason broken out in the multiple large-size lake body eutrophication problem set of China in recent years; Arsenate pollutes, and main generation is hidden in the To Mining Development and associated production technological process enriching area at arsenic minerals such as Guangxi, Hunan, Guizhou, has extremely strong toxicity, is classified as first kind carcinogenic substance by WHO; Fluorine ion generally results from mining industry or Ferrous Metallurgy is produced, and the underground water that fluorine ion exceeds standard can cause the disease such as fluorosis of bone, mottled teeth as drinking water source, and current China still has 7,000 ten thousand people drinking high-fluorine water; Humic acid is the main organic components in natural water body, the end products of animals and plants remains through various degradation, if through drinking water treatment chlorination flow process, then can produce the various halide that there is " three cause " and act on, therefore become the main pollutant paid close attention in drinking water pretreatment.
The removal of anionic pollutant in water, common method has bioanalysis, membrane filter method, chemical precipitation method etc.But aforementioned several method is very limited for the anionic pollutant removal effect of low concentration, cannot meet the quality standard of water environment of increasingly stringent.And absorption method, then there is the removal being applicable to low concentration pollutant, advantage of producing that sludge quantity is few, cost is low, treatment effect is stable etc., effectively can solve the problem that the removal of common process anionic pollutant cannot be up to standard.Have now been developed the diversified anion adsorbent for water treatment and using method thereof.
Zirconium, as a kind of transition metal, has good affinity and selective for anion such as phosphate radical, arsenate, fluorine ion and humic acid.The content of zr element in the earth's crust is 130mg/kg, higher than the metallic element that copper, zinc etc. are common, therefore has the feature being comparatively easy to obtain.In addition, zirconium content in human body is 250mg, thus also has biological safety.Based on above reason, zirconia and zirconium base adsorbent are widely used in water treatment field.China Patent Publication No. CN101555078A discloses the method for a kind of nano zircite except fluorine, fluoride waste is passed in the reaction tower loaded with nano zircite particle and carry out filtration absorption, water inlet 10mg/L, under flow velocity 9BV/h, water outlet 1mg/L, reaches discharge standard.But, nano zircite due to particle minimum, strainability is poor, and its efficiency of disposing of sewage is lower, can not meet the requirement of large-scale promotion.If it directly mixed with sewage, efficiency can significantly raise, but cannot solve absorption saturated after regeneration issues.Many researchers give solution to this, are carried on a series of matrix by zirconia particles, thus improve its strainability and ensure the recovery of adsorbent after absorption is saturated.Such as China Patent Publication No. CN102942239A discloses a kind of for the Polymers compound adsorbent except fluorine, by unformed zirconia load in the hole of styrene-divinylbenzene sphere polymers.This adsorbent produces preenrichment effect by polymer for fluorine ion, and fluorine ion to diffuse in hole and is fixed on hole inwall by diffusion, adsorbs afterwards in nano zircite particle surface generation obligate.Adsorb saturated adsorbent NaOH-NaCl mixed liquor to regenerate.The method can improve zirconic hydrodynamics well, and then promotes its strainability.Meanwhile, load also can make zirconic reference area expand, and promotes that it plays a role further., on any matrix, the amount of loaded zirconia is limited.Too much load may block dimeric hole, affects its strainability.Therefore, use matrix loaded zirconia, this thinking of filtrate that it can be used as purification anion to pollute, adsorption capacity still has limitation.
For the limitation of filtration method, can consider magnetic separation technique to be introduced in the making of zirconium base adsorbent.The magnetic-particle made as the particle of filtrate or modification of filtration medium adsorbent, has particle size little, the features such as specific area is large relatively, is thus conducive to absorption.Separation of Solid and Liquid can be carried out by externally-applied magnetic field after absorption terminates, also solve the problem of recovery.Existing magnetic adsorbent is generally (as Fe by the magnetic nanoparticle made
3o
4) use SiO
2carry out bag quilt, then utilize SiO
2further modification is carried out, with the needs of the applicable pollutant that will adsorb in the some position that surface is enriched.China Patent Publication No. CN104148008A discloses a kind of preparation method of the magnetic adsorbent for lead ion absorption.This technology is wrapped again by one deck titanium phosphate by the magnetic iron ore surface of silica at bag, is beneficial to the suction-operated of lead ion.Similar, China Patent Publication No. CN103065754A discloses a kind of wrapping by the magnetic iron ore pan coating benzene sulfonic acid of silica, in order to adsorb antibiotic adsorbent.Above two kinds of adsorbents all have received comparatively satisfied effect.Said method Problems existing is, the making of adsorbent needs three steps, complicated operation at least; Often use silane TEOS when wrapping oxidized silicon, it has inflammability and the toxicity to human body simultaneously, makes this type of technique to produce secondary pollution.
Summary of the invention
Object of the present invention is exactly provide a kind of preparation of the nano magnetic particle adsorbent for removing anionic pollutant in sewage to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for nano magnetic particle adsorbent, comprises the following steps:
(1) take trivalent iron salt, divalent iron salt and tetravalence zirconates and be placed in container, be dissolved in water obtained mixed aqueous solution;
(2) compound concentration is the alkali lye of 1.2 ~ 6mol/L, and under mechanical agitation, be added dropwise to by alkali lye in the obtained mixed aqueous solution of step (1), obtained pH value is the mixed liquor of 6.5 ~ 8.5;
(3) after dropping terminates, by mixed liquor ageing 10 ~ 20h at 45 ~ 75 DEG C, promote that its self assembly forms the ageing sample obtaining " shell-core " structure, wherein, magnetic iron ore is core, and zirconia is shell, and core is used for Magneto separate, and shell is used for adsorption fouling thing;
(4) by after ageing sample clean dry, object product adsorbent is namely obtained.
Described trivalent iron salt is iron chloride; Described divalent iron salt is ferrous sulfate; Described tetravalence zirconates is basic zirconium chloride or nitric acid oxidation zirconium.
In mixed aqueous solution described in step (1), ferric iron and ferrous atomic molar are than being 2:1, and the atomic molar ratio of iron and zirconium is 6 ~ 2:1.
Alkali lye described in step (2) is NaOH solution, and its concentration is 1.2 ~ 6mol/L.
In step (2), churned mechanically rotating speed is 200 ~ 500rpm, and the rate of addition of alkali lye is 0.05 ~ 5ml/min.
In step (4), the drying mode of ageing sample is oven dry, vacuum drying or freeze-drying.
The adsorbent that the present invention obtains, after absorption is saturated, by certain method desorption, realizes the resource of anionic pollutant, the sample of sorbent after desorption, and can recycle through regeneration, the method for adsorbent desorption and regeneration of the present invention is specific as follows:
A the saturated adsorbent of absorption mixes with the alkali lye of 0.5 ~ 3mol/L by (), the solid-to-liquid ratio of adsorbent and alkali lye is 1 ~ 5g/L, and then carry out desorption, desorption time is 4 ~ 10h, and after desorption completes, Separation of Solid and Liquid obtains the sample of sorbent of desorption;
B adsorbent after desorption mixes with water by (), obtain mixed liquor, drips H
+concentration is that mixed liquor is recalled to certain pH value by the acid solution of 0.01 ~ 1mol/L, this pH value be adsorbent adsorb use before mix with water gaging such as grade time pH;
C (), by mixed liquor Separation of Solid and Liquid, after solid water cleans up, can enter next round and use.
The nano magnetic particle adsorbent that the present invention obtains has goodish magnetic (>20emu/g), can realize quick Magneto separate and the recovery of the adsorbent after adsorbing.Be more than 1mmol/g to the saturated extent of adsorption of adsorbent, to the anionic pollutant of low concentration, there is lasting purification function, use repeatedly that still water outlet still can be up to standard.By controlling more than 6.5 by titration end-point, ensure that the formation of the magnetite cores with good crystal formation; Unformed hydrous zirconium oxide(HZO) is due to structure relative loose, be wrapped in the outside of magnetic iron ore nucleus, structure that self assembly defines " shell-core ", the zirconia that this structure is very beneficial for adsorption capacity stronger plays a role at adsorbent surface, ensure the magnetic of adsorbent itself simultaneously, and according to the characteristic of Anion-adsorption, if the too high meeting of titration end-point makes the surface presentation of magnetic oxygenated zirconium alkaline during synthesis sorbing material, be unfavorable for the absorption of anion, therefore the upper limit of titration end-point is defined as 8.5.During synthesizing magnetic granule adsorbent, the mol ratio of Fe atom and Zr atom is controlled at 6 ~ 2:1, ensure that magnetic and the absorption property of magnetic-particle sorbent material, both can not be difficult to ensure because of the too low magnetic of material that makes of magnetic iron ore ratio, again can not cannot complete oxidized zirconium bag quilt because of the too low material surface that makes of zirconic ratio, affect its adsorption capacity.
Compared with prior art, the present invention has the following advantages:
1) cost is low: zirconates, molysite and NaOH that the present invention is used cheap, and preparation method's condition is easy to control;
2) absorption property is excellent, recyclable: the magnetic nano zircite adsorbent of the tool that the present invention obtains, both make use of zirconic strong adsorption capacity, realize the removal to multiple anionic pollutant, rely on the magnetic iron ore in adsorbent to ensure that its reclaiming simultaneously;
3) technological process is simple: obtain traditional three-step approach by one-step method and obtain " shell-core " structure, the stronger adsorption capacity zirconia part that has in magnetic oxygenated zirconium is made to be in sorbent particle surfaces, and magnetic iron ore part is positioned at absorbent particles inside, obtain easily separated, efficient by simple method, saturated rear repeatedly used adsorbent;
4) pollution-free: without any need for organic solvent and toxic reagent in preparation process, to there is environment friendly;
5) adsorbent is after absorption is saturated, and by certain method desorption, the resource realizing anionic pollutant reclaims.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention;
Fig. 2 is the transmission electron microscope picture of adsorbent obtained in embodiments of the invention 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.The present embodiment is implemented premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
As shown in Figure 1, by 0.5mol FeSO
47H
2o, 1mol FeCl
36H
2o and 0.4mol ZrOCl
28H
2o, is made into 500ml mixed aqueous solution.With the speed of 400 revs/min, mechanical agitation is applied to this aqueous solution, then 6mol/L NaOH solution is dripped to mixed aqueous solution pH=7.6, half an hour is stirred again after adding, again by this mixed aqueous solution ageing 12h at 60 DEG C, adopt magnetic separation technique to be separated 10min to mixed liquor afterwards and carry out Separation of Solid and Liquid, after obtaining the cleaning of solid portion water, dry, namely obtain object product adsorbent.
Transmission electron microscope (TEM) scanning is carried out to obtained adsorbent, finds that adsorbent defines " shell-core " structure that unformed hydrous zirconium oxide(HZO) is wrapped in the outside of magnetic iron ore nucleus, as shown in Figure 2.
Adopt above-mentioned adsorbent to carry out Shanghai Sewage Plant secondary biochemical treatment tail water dephosphorization, result shows:
(1) adsorbent is 42mg/g to phosphatic maximal absorptive capacity;
(2) saturation magnetization of adsorbent is 25emu/g, can realize quick Magneto separate by magnetic field;
(3) reaction time of 0.5h is ensured, the dosage of 1kg/ ton, in the sewage (with the configuration of Shanghai district running water) of 2mg P/L, runs 7 times, water outlet phosphorus concentration is all less than 0.5mg/L, meets country for the one-level A standard about phosphorus in the draining of town sewage plant secondary effluent;
(4) adsorb saturated adsorbent, with the NaOH solution desorption of 1mol/L and after regeneration, saturated extent of adsorption still has original more than 90%, and still can maintain this level after regeneration repeatedly.
Adopt above-mentioned adsorbent, somewhere, Beijing Fluorine Containing Groundwater is purified.Former inundation manage is 3.01mg/L, and this adsorbent, under the throwing amount of 1g/L, namely can realize the removal of more than 90%, runs repeatedly stable water outlet at below national standard 1mg/L.
Embodiment 2
In absorbent preparation process, except ZrOCl
28H
2the dosage of O is outside 0.6mol, and other are all identical with embodiment 1.
Saturation magnetization test is carried out to above-mentioned obtained adsorbent, finds that the saturation magnetization of this adsorbent is 23emu/g; The test of trivalent arsenic hydrochlorate pollutant purification is carried out to adsorbent, finds that adsorbent is 116mg/g to the maximal absorptive capacity of trivalent arsenic hydrochlorate.
This adsorbent is adopted to purify somewhere, the Inner Mongol underground water that arsenate exceeds standard.In former water, the content of arsenic is 0.33mg/L, and main component is trivalent arsenic.Under the throwing amount of 1kg/ ton, after 1h reaction, the aqueous concentration of arsenic is lower than 0.05mg/L, meets national standard.This adsorbent is repeatedly to run water outlet under the condition of 3 times up to standard all the time.And can continue to use after desorption and regeneration.
Embodiment 3
A preparation method for nano magnetic particle adsorbent, its preparation flow, see Fig. 1, comprises the following steps:
(1) respectively by 1molFeSO
47H
2o, 2molFeCl
36H
2o and 0.5mol ZrOCl
28H
2o is placed in container, and be dissolved in water obtained mixed aqueous solution;
(2) compound concentration is the NaOH solution of 1.2mol/L, be under the mechanical agitation of 200rpm at rotating speed, NaOH solution added in the obtained mixed aqueous solution of step (1) with the rate of addition of 5ml/min, obtained pH value is the mixed liquor of 6.5;
(3) after dropping terminates, by mixed liquor ageing 20h at 45 DEG C, promote that its self assembly forms the ageing sample obtaining " shell-core " structure, wherein, magnetic iron ore is core, and zirconia is shell, and core is used for Magneto separate, and shell is used for adsorption fouling thing;
(4) by ageing sample separation out, clean post-drying, namely obtain object product adsorbent.
Embodiment 4
A preparation method for nano magnetic particle adsorbent, comprises the following steps:
(1) respectively by 1molFeSO
47H
2o, 2molFeCl
36H
2o and 1.5mol ZrOCl
28H
2o is placed in container, and be dissolved in water obtained mixed aqueous solution;
(2) compound concentration is the NaOH solution of 6mol/L, be under the mechanical agitation of 500rpm at rotating speed, NaOH solution added in the obtained mixed aqueous solution of step (1) with the rate of addition of 0.05ml/min, obtained pH value is the mixed liquor of 8.5;
(3) after dropping terminates, by mixed liquor ageing 10h at 75 DEG C, promote that its self assembly forms the ageing sample obtaining " shell-core " structure, wherein, magnetic iron ore is core, and zirconia is shell, and core is used for Magneto separate, and shell is used for adsorption fouling thing;
(4) by ageing sample separation out, clean final vacuum dry, namely obtain object product adsorbent.
Embodiment 5
A preparation method for nano magnetic particle adsorbent, comprises the following steps:
(1) respectively by 1molFeSO
47H
2o, 2molFeCl
36H
2o and 1mol ZrO (NO
3)
2h
2o is placed in container, and be dissolved in water obtained mixed aqueous solution;
(2) compound concentration is the NaOH solution of 3mol/L, is under the mechanical agitation of 300rpm at rotating speed, and NaOH solution added in the obtained mixed aqueous solution of step (1) with the rate of addition of 2ml/min, obtained pH value is the mixed liquor of 7.5;
(3) after dropping terminates, by mixed liquor ageing 15h at 65 DEG C, promote that its self assembly forms the ageing sample obtaining " shell-core " structure, wherein, magnetic iron ore is core, and zirconia is shell, and core is used for Magneto separate, and shell is used for adsorption fouling thing;
(4) by ageing sample separation out, freeze-drying after cleaning, namely obtains object product adsorbent.
Claims (6)
1. a preparation method for nano magnetic particle adsorbent, is characterized in that, comprises the following steps:
(1) take trivalent iron salt, divalent iron salt and tetravalence zirconates and be placed in container, be dissolved in water obtained mixed aqueous solution;
(2) under mechanical agitation, be added dropwise to by alkali lye in the obtained mixed aqueous solution of step (1), obtained pH value is the mixed liquor of 6.5 ~ 8.5;
(3), after dropping terminates, by mixed liquor ageing 10 ~ 20h at 45 ~ 75 DEG C, ageing sample after Separation of Solid and Liquid, is obtained;
(4) by after ageing sample clean dry, object product adsorbent is namely obtained.
2. the preparation method of a kind of nano magnetic particle adsorbent according to claim 1, is characterized in that, described trivalent iron salt is iron chloride; Described divalent iron salt is ferrous sulfate; Described tetravalence zirconates is basic zirconium chloride or nitric acid oxidation zirconium.
3. the preparation method of a kind of nano magnetic particle adsorbent according to claim 1, it is characterized in that, in mixed aqueous solution described in step (1), ferric iron and ferrous atomic molar are than being 2:1, and the atomic molar ratio of iron and zirconium is 6 ~ 2:1.
4. the preparation method of a kind of nano magnetic particle adsorbent according to claim 1, is characterized in that, the alkali lye described in step (2) is NaOH solution, and its concentration is 1.2 ~ 6mol/L.
5. the preparation method of a kind of nano magnetic particle adsorbent according to claim 1, is characterized in that, in step (2), churned mechanically rotating speed is 200 ~ 500rpm, and the rate of addition of alkali lye is 0.05 ~ 5ml/min.
6. the preparation method of a kind of nano magnetic particle adsorbent according to claim 1, is characterized in that, in step (4), the drying mode of ageing sample is oven dry, vacuum drying or freeze-drying.
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Cited By (5)
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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 |
| CN117551016A (en) * | 2024-01-11 | 2024-02-13 | 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN117551016A (en) * | 2024-01-11 | 2024-02-13 | 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 |
| 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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