CN104826600B - A kind of magnetic kleit preparation method - Google Patents
A kind of magnetic kleit preparation method Download PDFInfo
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- CN104826600B CN104826600B CN201510222142.7A CN201510222142A CN104826600B CN 104826600 B CN104826600 B CN 104826600B CN 201510222142 A CN201510222142 A CN 201510222142A CN 104826600 B CN104826600 B CN 104826600B
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Abstract
The present invention relates to a kind of magnetic kleit preparation method, belong to water technology, inorganic composite materials and technical field.The method of the present invention is by FeCl3∙6H2O、NaAc∙3H2O, ethylene glycol, ethylenediamine shape and the mixed yellowish-brown suspension of kaolin are packaged in ptfe autoclave, and more than 8h is reacted under the conditions of 180 200 DEG C, black solid washing, Magneto separate, drying, grinding, sieving is taken, obtains magnetic kaolin.Directly kaolin is carried out by Hydrothermal Synthesiss technology by the present invention plus magnetic is modified, and method is simple and easy to control, and preparation cost is low, and industrialized production threshold is low, is easy to industrialization promotion；And this method temperature is low, kaolinic structure will not be destroyed, it is ensured that its absorption property；There is preferable removal effect to the phosphate in water, and the quick separating of solid-liquid can be achieved after the completion of absorption, adsorbent is separated from adsorbent solution, recycled.
Description
Technical field
The present invention relates to a kind of magnetic kleit preparation method, belong to water technology, inorganic composite materials and technology
Field.
Background technology
Kaolin is that one kind has layer structure clay mineral, is that main component is kaolinic porous material.Kaolinite
Stone is dioctahedron 1:1 type layer silicate mineral, exist with atomic small crystallite or cryptocrystal state, and with compact massive or
Earthy aggregate produces, and chemical composition is：Al[Si4O10](OH)8, the layer silicate mineral of crystal category anorthic system.
Kaolin has huge specific surface area, good adsorption properties and ion-exchange performance.With plasticity, higher
Fire resistance, good insulating properties and chemical stability, previous studies be concentrated mainly on ceramics, refractory material, rubber, medicine,
The fields such as cosmetics.Because its particle surface has fine pore, there is certain adsorptivity, be a kind of high-quality cheap absorption
Agent, many fields such as environmental protection, chemistry, agricultural have been widely used in it.
In recent years, using kaolinic Study on adsorption properties, its application in field of waste water treatment achieves good effect
Fruit, in order to further improve kaolin absorption property, researcher mainly uses Physical or chemical method both at home and abroad at present, such as acid
The modes such as leaching, roasting, organic intercalation, polyalcohol intercalation and inorganic-organic hybrid are modified to it, and what is also had is processed further
Molecular sieve is made, so that its surface nature and interlayer structure are changed, increases its adsorption capacity.Modified kaolin has because of it
The physicochemical property such as have good plasticity, antiacid dissolubility, fire resistance, specific surface area big and be widely used.It is phosphorous, again handling
There is extensive and good application in metallic wastewater, organic wastewater and waste water from dyestuff.
Magnetic carrier technology, be will be scattered have ferromagnetic substance be uniformly introduced into non magnetic or weak magnetic particle from
And strengthen the magnetic susceptibility of matrix material, then using magnetic separation technique by the magnetic compound of saturation from effect system it is fast
The separation of speed.It is combined with mineral material can not only change the interlayer structure of mineral material, and can also make mineral material
Recovery is reused.At present, magnetic carrier technology is combined with kaolin and prepares magnetic kaolin material, prepared
The method of magnetic kaolin material includes coprecipitation and the major class of hydro-thermal method two.Wherein coprecipitation refers to contain two in the solution
Kind or a variety of cations, they add precipitating reagent, after precipitation reaction, can obtain various composition homogeneously to exist in solution
Homogeneous precipitation, then precipitation is dried and calcined, so as to obtain high purity nanometer powders material.Such as
CN103721671A discloses a kind of nano magnetic iron oxide/kaolin particle and its production and use：Dissolving poly- second
In the bath solution of alkene pyrrolidone, kaolin is first added（Sodium hydroxide adjusts pH）, then it is separately added into a certain amount of ferrous iron
Salt and molysite, brownish black precipitation is produced, alkali lye is continuously added during reaction and adjusts pH 10 or so.It is dried in vacuo after reaction, most
After pulverize sieving be made nano magnetic iron oxide/kaolin particle.The coreshell type structure of the particle kernel and shell, its kernel are
Kaolin mineral, shell are nano magnetic iron oxide（Fe3O4）, can efficiently remove the polluters such as arsenic in water body.
The preparation principle of hydro-thermal method refers in the pressure vessel of sealing（Autoclave）, in the condition of HTHP
Under, metal ion hydrolyzes to form metal oxide deposits in alkaline environment, and the sediment purity is higher, and particle is thinner.
Such as CN103566866A discloses a kind of method that magnetic 4A molecular sieves are prepared using kaolin：With Fe3O4For magnetic carrier,
For kaolin as raw material, aluminium hydroxide is supplement silicon source, is prepared by hydrothermal synthesis method cheap, high-performance, recoverable
Magnetic 4A molecular sieves.The 4A magnetic zeolite Size of Zeolite of synthesis is thin, magnetic stability is good, all has to ammonia nitrogen and heavy metal contaminants
There is higher clearance.
The content of the invention
It is an object of the invention to provide a kind of efficiency high, technique is simple, has the magnetic kaolin of stronger absorption property
Preparation method, and for removing water pollutant.
Technical scheme
A kind of magnetic kleit preparation method, comprises the following steps：
（1）By FeCl3∙6H2O、NaAc∙3H2O is dissolved in ethylene glycol, then adds ethylenediamine and forms clear solution, adds
Kaolin, obtain yellowish-brown suspension；
（2）Suspension is packaged in ptfe autoclave, more than 8h is reacted under the conditions of 180-200 DEG C, is taken black
Color solid；
（3）Black solid is scrubbed, Magneto separate, drying, grinding, sieving, obtain magnetic kaolin.
The preparation method of the present invention is carried out using iron chloride as source of iron using ethylene glycol as solvent and to ferric ion
Partial solvent heat-treats, and successfully synthesizes ferroferric oxide nano granules；Use sodium acetate as reflection auxiliary agent, ethylenediamine for parcel
Agent, by controlling the ratio of ethylenediamine and ferric trichloride can be with the ferroso-ferric oxide of the homogeneous nanometer of compound particle size.Synthesizing
It is as follows by two step key reactions, possible reaction in the reaction of ferroferric oxide nano granules：
2Fe3++OHCH2CH2OH+2H+ →2Fe2++CH3CHO+2H2O；
2Fe3++Fe2++8OH- →Fe3O4+4H2O。
The ferroferric oxide nano granules of synthesis combine to form magnetic kaolin with kaolin.
In addition, ethylenediamine will add again after first three reagent adds；Otherwise, iron chloride and sodium acetate can not dissolve.
In the above method, FeCl3∙6H2O, ethylene glycol, NaAc 3H2O, it is kaolinic to participate in magnetic for ethylenediamine and kaolin
Building-up process, the change of its dosage have no effect on the generation of product, but can influence the prepared kaolinic performance of magnetic.For
Reduce the magnetic kaolin that wastage of material obtains higher magnetic simultaneously, FeCl3∙6H2O, ethylene glycol, NaAc 3H2O, ethylenediamine
It is preferably with kaolinic usage ratio：1.0 g：20 mL：3.0 g：10 mL：0.1-1.0 g；Most preferably：1.0 g：
20 mL：3.0 g：10 mL：0.4 g.
In order to shorten mixing time, the above method, preferably by FeCl3∙6H2O is dissolved in ethylene glycol, is then added
NaAc∙3H2O。
Beneficial effect
（1）Directly kaolin is carried out by Hydrothermal Synthesiss technology by the present invention plus magnetic is modified, and method is simple and easy to control, is prepared into
This is low, and industrialized production threshold is low, is easy to industrialization promotion；
（2）This method of modifying temperature is low, will not destroy kaolinic structure, it is ensured that its absorption property；
（3）Ethylenediamine is added in preparation process, the absorption property and superparamagnetism of product can be significantly improved；
（4）There is preferable removal effect to the phosphate in water, and the quick of solid-liquid can be achieved after the completion of absorption
Separation, makes adsorbent be separated from adsorbent solution, is recycled, and partial contamination thing can also be recycled, protection
The sustainability of resource is promoted while environment.
Brief description of the drawings
Fig. 1 is the magnetic kaolin and kaolin original soil, Fe of the present invention3O4The X-ray diffraction spectra figure of contrast；Wherein, A-
E is followed successively by：Kaolin original soil, Fe3O4, embodiment 2-4 the kaolinic X-ray diffraction spectra figure of magnetic.
Embodiment
Embodiment 1
（1）By 2.0 g FeCl3∙6H2O is dissolved in 40 mL ethylene glycol, then adds 6.0 g NaAc 3H2O and 20
ML ethylenediamines, add 0.2 g kaolin, and 30 min of stirring make its fully dispersed；
（2）Said mixture is encapsulated in the reactor of polytetrafluoroethylene (PTFE), 8 h are reacted at 200 DEG C, it is cold after the completion of reaction
But room temperature is arrived；
（3）By obtained black solid with water washing is distilled for several times, Magneto separate, dry, grind, sieving, obtain magnetic height
Ridge soil MK1；
At room temperature, 0.1 g MK1 are added in the mg/L of 25 mL 20 phosphate solution, vibrate 120 min, absorption
Rate reaches 91.57%；Under the same terms, kaolin original soil is only 3.18% to phosphatic adsorption rate.
Embodiment 2
（1）By 2.0 g FeCl3∙6H2O is dissolved in 40 mL ethylene glycol, then adds 6.0 g NaAc 3H2O and 20
ML ethylenediamines, add 0.4 g kaolin, and 30 min of stirring make its fully dispersed；
（2）Said mixture is encapsulated in the reactor of polytetrafluoroethylene (PTFE), 8 h are reacted at 200 DEG C, it is cold after the completion of reaction
But room temperature is arrived；
（3）By obtained black solid with water washing is distilled for several times, Magneto separate, dry, grind, sieving, obtain magnetic height
Ridge soil MK2；
At room temperature, 0.1 g MK2 are added in the mg/L of 25 mL 20 phosphate solution, vibrate 120 min, absorption
Rate reaches 91.39%；Under the same terms, kaolin original soil is only 3.18% to phosphatic adsorption rate.
Embodiment 3
（1）By 2.0 g FeCl3∙6H2O is dissolved in 40 mL ethylene glycol, then adds 6.0 g NaAc 3H2O and 20
ML ethylenediamines, add 0.8 g kaolin, and 30 min of stirring make its fully dispersed；
（2）Said mixture is encapsulated in the reactor of polytetrafluoroethylene (PTFE), 8 h are reacted at 200 DEG C, it is cold after the completion of reaction
But room temperature is arrived；
（3）By obtained black solid with water washing is distilled for several times, Magneto separate, dry, grind, sieving, obtain magnetic height
Ridge soil MK3；
At room temperature, 0.1 g MK3 are added in the mg/L of 25 mL 20 phosphate solution, vibrate 120 min, absorption
Rate reaches 92.70%；Under the same terms, kaolin original soil is only 3.18% to phosphatic adsorption rate.
Embodiment 4
（1）By 2.0 g FeCl3∙6H2O is dissolved in 40mL ethylene glycol, then adds 6.0 g NaAc 3H2O and 20 mL
Ethylenediamine, adds 2.0 g kaolin, and 30 min of stirring make its fully dispersed；
（2）Said mixture is encapsulated in the reactor of polytetrafluoroethylene (PTFE), 8 h are reacted at 200 DEG C, it is cold after the completion of reaction
But room temperature is arrived；
（3）By obtained black solid with water washing is distilled for several times, Magneto separate, dry, grind, sieving, obtain magnetic height
Ridge soil MK4；
At room temperature, 0.1 g MK4 are added in the mg/L of 25 mL 20 phosphate solution, vibrate 120 min, absorption
Rate reaches 89.70%；Under the same terms, kaolin original soil is only 3.18% to phosphatic adsorption rate.
Embodiment 5
（1）By 2.0 g FeCl3∙6H2O is dissolved in 40 mL ethylene glycol, then adds 6.0 g NaAc 3H2O, then add
Enter 0.8 g kaolin, 30 min of stirring make its fully dispersed；
（2）Said mixture is encapsulated in the reactor of polytetrafluoroethylene (PTFE), 8 h are reacted at 200 DEG C, it is cold after the completion of reaction
But room temperature is arrived；
（3）By obtained black solid with water washing is distilled for several times, Magneto separate, dry, grind, sieving, obtain magnetic height
Ridge soil MK5；
At room temperature, 0.1 g MK5 are added in the mg/L of 25 mL 20 phosphate solution, vibrate 120 min, absorption
Rate reaches 38.90%.
The experimental data of comparing embodiment 3 and embodiment 5 can be drawn, in the case of other conditions identical, prepared
During add ethylenediamine prepare magnetic kaolin MK3 absorption property, hence it is evident that be higher than, second be not added with preparation process
Magnetic kaolin MK5 prepared by diamines absorption property.As can be seen here, ethylenediamine serves in the preparation process in accordance with the present invention
Improve the effect of product absorption property.
The present invention has found in experimentation：With the increase of kaolinic amount, Fe and kaolinic ratio（Fe/ kaolinites
Soil）Smaller, the magnetism of material of synthesis is weaker.MK3 superparamagnetism energy（With the increase of externally-applied magnetic field, the increased property of magnetic
Energy）Stronger than MK5, energy consumption is smaller in magnetic history；So addition ethylenediamine can strengthen the kaolinic superparamagnetism of magnetic
Can, reduce the energy loss during remagnetization.
Claims (2)
1. a kind of magnetic kaolin is used for the phosphatic method gone in water removal, comprise the following steps：
(1) by FeCl3·6H2O is dissolved in ethylene glycol, then adds NaAc3H2O, then add ethylenediamine formed it is transparent molten
Liquid, kaolin is added, obtain yellowish-brown suspension；FeCl3·6H2O, ethylene glycol, NaAc3H2O, ethylenediamine and kaolinic
Usage ratio is：1.0g：20mL：3.0g：10mL：0.1-1.0g；
(2) suspension is packaged in ptfe autoclave, 8h is reacted under the conditions of 180-200 DEG C, take black solid；
(3) black solid is scrubbed, Magneto separate, drying, grinding, sieving, obtain magnetic kaolin；
(4) 0.1g magnetic kaolin is added in 25mL 20mg/L phosphate solution, vibrated, absorption.
2. according to the method for claim 1, it is characterised in that FeCl3·6H2O, ethylene glycol, NaAc3H2O, ethylenediamine
It is with kaolinic usage ratio：1.0g：20mL：3.0g：10mL：0.4g.
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| CN105413630A (en) * | 2016-01-21 | 2016-03-23 | 齐齐哈尔大学 | Magnetic medical stone composite adsorption material and preparing method thereof |
| CN106693886A (en) * | 2016-12-27 | 2017-05-24 | 高州市兆翔新材料有限公司 | Preparation method of magnetic nanometer kaolin for underground water treatment |
| CN110180497A (en) * | 2019-05-27 | 2019-08-30 | 广西壮族自治区农业科学院 | The preparation method of the magnetic material of methyl blue in a kind of absorption effluent |
| CN111389376A (en) * | 2020-03-03 | 2020-07-10 | 苏州科技大学 | Polypyrrole-modified magnetic kaolin nanocomposite and preparation method and application thereof |
| CN111547777B (en) * | 2020-05-22 | 2022-01-28 | 昆明理工大学 | Method for removing arsenic in contaminated acid by ferroferric oxide/kaolin nanocomposite |
| CN114700058B (en) * | 2022-04-29 | 2023-09-19 | 新疆师范大学 | Preparation method of porous magnetic composite adsorbent and application of porous magnetic composite adsorbent in adsorption of dimethyl arsonic acid |
| CN116040731B (en) * | 2023-01-31 | 2023-11-10 | 广东名桂环保有限公司 | Composite water treatment agent and preparation method thereof |
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| US7291271B2 (en) * | 2003-12-09 | 2007-11-06 | Separation Design Group, Llc | Meso-frequency traveling wave electro-kinetic continuous adsorption system |
| CN1300006C (en) * | 2005-03-24 | 2007-02-14 | 浙江大学 | Prepn process of magnetic composite organic bentonite as water treating material |
| CN100469436C (en) * | 2006-06-06 | 2009-03-18 | 河北工业大学 | Bentonite for purifying water and its preparation |
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