CN109794222A - A kind of organic decoration Magnetic Bentonite and its preparation method and application - Google Patents
A kind of organic decoration Magnetic Bentonite and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of organic decoration Magnetic Bentonite and its preparation method and application, and magnetic Nano Fe is prepared using microwave coprecipitation method3O4It is loaded on natural montmorillonite after particle, and cetyl trimethylammonium bromide is used to be surface modified as organic modifier, obtain organic decoration Magnetic Bentonite.The organic decoration Magnetic Bentonite thermal stability being prepared is good, can keep stable structure in the range of temperature is 300-700 DEG C；It is not easy to be destroyed by strong oxidizer, strong reductant, there is good chemical stability；Hole holds aperture increases, good to Congo red and acid scarlet adsorption effect；It may be implemented quickly to recycle under the action of externally-applied magnetic field, there is good recycling rate of waterused and stable performance.
Description
Technical field
The invention belongs to bentonite deep process technology fields, and in particular to a kind of organic decoration Magnetic Bentonite and its preparation
Methods and applications.
Background technique
In recent years, the textile and dyeing industry in China is grown rapidly, and produces the waste water from dyestuff for largely needing processing.Generalization
Learning dyestuff often has the characteristics such as acidproof, alkaline-resisting, difficult to degrade, influences the gene genetic of aquatic animals and plants, seriously threatens its existence,
It is also possible to threatening the life of the mankind.Wherein, Congo red (CR) and acid scarlet (GR) belong to anionic dyes, do not dissolve in
Bronsted lowry acids and bases bronsted lowry can not only inhibit the growth and development of animals and plants once being just difficult to remove into nature, at the same to the digestion of the mankind,
Blood and cardiovascular system cause different degrees of influence.
Clay mineral resource one of of the bentonite (Bentonite) as China's rich reserves, it is cheap, have very big
Development and utilization and researching value.Bentonite is mainly made of aqueous lamellar aluminosilicate, and basic performance is by the special of montmorillonite
Structure determines.The structure of montmorillonite determines bentonitic decolourising property, stability, ion exchangeable, adsorptivity, suspension etc.,
Bentonitic inner ratio surface area is 600-800m2/ g, the bentonite volume energy after water suction increase 10-30 times, have one to dyestuff
Fixed absorption property；But non-modified natural montmorillonite (Raw Bentonite, RB) is poor to the absorption property of dyestuff,
And its in water stronger dispersibility also make absorption after bentonite be difficult to realize effectively be separated by solid-liquid separation, it is therefore necessary to swelling
Soil carries out organically-modified or load Fe3O4Equal magnetisable materials, to improve its absorption property and solid-liquid separation capability.
Magnetic carrier refer to by the covering of the ferromagnetic substance of good dispersion property or be introduced into it is non magnetic or weak magnetic material
The surface or inside of material, and then the composite material with certain magnetic saturation intensity is formed, it can be under the action of externally-applied magnetic field
It is quickly separated by solid-liquid separation to recycling and reusing.Nanometer Fe3O4Particle is relatively conventional one of magnetic material, synthesis technology letter
It is single, possess good Magneto separate performance, and nanometer Fe3O4Particle itself has certain adsorption capacity.But nanometer Fe3O4
Particle is easy to reunite, oxidizable, and performance is unstable, and bentonite has good dispersibility in water body, therefore, by bentonite and
Nanometer Fe3O4Particle combines, and prepares Magnetic Bentonite (Magnetic bentonite, MB), can not only solve nanometer
Fe3O4Particle is easy to reunite, oxidizable, the unstable problem of performance, moreover it is possible to improve bentonitic solid-liquid separation capability, while can be
Improve its adsorption capacity to dyestuff to a certain extent: Wang Yingya etc. prepares nanometer Fe with the precipitation method3O4Particle, then by it
It is attached on alkaline calcium bentonite, then is modified with citric acid, prepare the bentonitic compound of magnetic citric acid, magnetic
Good separating effect, and there is good adsorption effect to Cr (VI)；Appoint refreshing wait that Fe is added in bentonite suspension2(SO4)3With
FeSO4, negative (sun) ion compounding dressing agent is added, negative (sun) ion compounding modification both sexes Magnetic Bentonite is prepared, it is compound
The specific surface area of object and hole hold empty diameter and significantly increase, and the adsorption effect of Pyrogentisinic Acid also obviously rises, and adsorption capacity reaches
491.61mg/g。
Currently used for the nanometer Fe in conjunction with bentonite3O4Particle is modified by surface reactive material.Single
Nanometer Fe3O4Although particle can improve bentonitic solid-liquid separation capability to a certain extent, have to the adsorption capacity of dyestuff
Limit；In addition, the nanometer Fe not being modified3O4Particle is easily oxidized and loses part magnetism, therefore, simple nanometer Fe3O4
Particle modification bentonite and the magnetic soil formed not only the adsorption effect of dyestuff is promoted it is few, but also since its magnetism is easily by oxygen
Change, so solid-liquid separation effect is also bad.There is correlative study to show nanometer Fe3O4Particle is through hydroxyl (- OH), amino (- NH2)
Etc. can not only carry out effective protection after group modified to magnetic core, but also it has clear improvement to the adsorption capacity of dyestuff.Therefore,
Chemically modified chemical group is supported on nanometer Fe3O4It is combined again with bentonite on particle, not only can protect nanometer
Fe3O4Particle avoids magnetic core from failing, and can effectively improve compound to the adsorption effect of dyestuff: Wu Mingxia etc. is using coprecipitated
Shallow lake method prepares Fe3O4Magnetic fluid prepares Fe with magnetic fluid and the composite modified organobentonite of disodium ethylene diamine tetraacetate3O4Load
Modified magnetic organobentonite, the composite material thermal stability is strong, in conjunction with rear performance stablize, to the radioactive nucleus on nuclear equipment
Plain adsorption capacity enhancing, Langmuir adsorption capacity have reached 297mg/g.
So far, study the most of organically-modified Magnetic Bentonites prepared be for handling heavy metal solution,
Thus stronger heavy metal ion adsorbed performance is shown, and the modified alta-mud for being specifically used to adsorb certain a class of dyes
Rarely found, and general modified alta-mud is not high to the adsorption effect of dyestuff: Chen Wangxiang etc. is by by cetyl trimethyl
Ammonium bromide (CTMAB) and chitosan (CTS) composite modified vermiculite as a kind of new adsorbent material, concrete operation step be by
A certain amount of chitosan is dissolved in the glacial acetic acid solution that volume fraction is 5%, and it is molten to be configured to the chitosan that volume fraction is 1%
The cetyl trimethylammonium bromide solution of certain volume is added until completely dissolved, obtains CTMAB/CTS composite solution for liquid,
It is eventually adding the vermiculite original soil that crushed 60-80 mesh, holding solid-liquid mass ratio is 1:10, obtains the bis- modified leech of CTMAB/CTS
Stone only has 29mg/g to the Langmuir adsorption capacity of acid scarlet.As it can be seen that the selection of organic surface modification agent is for dyestuff
Adsorption rate it is most important.Magnetic Bentonite is modified therefore, it is necessary to explore a kind of suitable organic modifiers, is improved
Adsorption effect of the modified alta-mud to Congo red (CR) and acid scarlet (GR).
Summary of the invention
In view of the problems of the existing technology, the present invention provide a kind of organic decoration Magnetic Bentonite and preparation method thereof and
Using magnetic Nano Fe is prepared using microwave coprecipitation method in the present invention3O4It is loaded on natural montmorillonite after particle,
And cetyl trimethylammonium bromide is used to be surface modified as organic modifier, obtain organic decoration Magnetic Bentonite.System
Standby obtained organic decoration Magnetic Bentonite hydrophily and good dispersion, thermal stability is good, and chemical stability is good, to Congo red
It is good with the adsorption effect of acid scarlet, it may be implemented quickly to recycle under the action of externally-applied magnetic field, have and repeat benefit well
With rate and stable performance.
Technical scheme is as follows:
A kind of preparation method of organic decoration Magnetic Bentonite, this method are as follows: magnetic is prepared using microwave coprecipitation method
Property nanometer Fe3O4It is loaded to after particle on natural montmorillonite (RB), obtains Magnetic Bentonite (MB), with cetyl front three
Base ammonium bromide (CTAB) is surface modified Magnetic Bentonite as organic modifier, and organic decoration magnetism swelling can be obtained
Native (CTAB/MB).
As a preferred option of the technical scheme, the method specifically includes the following steps:
(1)Fe3O4The preparation of magnetic fluid: by FeCl3·6H2O and FeCl2·4H2After O dissolution completely, first microwave preheating, so
After ammonium hydroxide is added, then carry out microwave heating reaction, then ageing stirring, obtains Fe3O4Magnetic fluid；
(2) preparation of mixed dispersion liquid: cetyl trimethylammonium bromide and natural montmorillonite is soluble in water, ultrasound point
It dissipates, obtains mixed dispersion liquid；
(3) Fe the preparation of organic decoration Magnetic Bentonite: is added in mixed dispersion liquid3O4In magnetic fluid, suspension is obtained,
Then microwave heating reaction is carried out, is cooled to room temperature after reaction, being washed out to the pH of suspension is 7-8, then vacuum is done
It is dry to get organic decoration Magnetic Bentonite (CTAB/MB).
The process flow chart that the present invention prepares organic decoration Magnetic Bentonite (CTAB/MB) is as shown in Figure 3.
As a preferred option of the technical scheme, the mass ratio of the cetyl trimethylammonium bromide and natural montmorillonite is 1:1-
1:2。
As a preferred option of the technical scheme, the FeCl3·6H2O and FeCl2·4H2The ratio between amount of substance of O is 1.6:1-
2:1。
As a preferred option of the technical scheme, the Fe3O4Fe in magnetic fluid3O4Quality be cetyl trimethylammonium bromide
With the 5-20% of the quality sum of natural montmorillonite.
As a preferred option of the technical scheme, stirring, stirring rate 300-450rpmmin are cooperated when the microwave reaction-1；
In the step (1), microwave reaction condition are as follows: microwave preheating stage 3-5min, microwave heating stage 30-40min, microwave parameters
Are as follows: 60 DEG C, 600W, mixed phase (0)；In the step (3), microwave reaction condition are as follows: 2-4h, microwave parameters are reacted in microwave heating
Are as follows: 60 DEG C, 600W, mixed phase (0).
As a preferred option of the technical scheme, the vacuum drying temperature is 60 DEG C, time 8-12h.
Further, structure determination is carried out to obtained organic decoration Magnetic Bentonite (CTAB/MB) made above, this has
It is load matrix, carried magnetic nano Fe that machine maintenance decorations Magnetic Bentonite, which is with natural montmorillonite,3O4Particle, and use organic modifier
A kind of trielement composite material that cetyl trimethylammonium bromide is surface modified, structure are as shown in Figure 1；Interlayer in Fig. 1
Shape object indicates natural montmorillonite, and substance is simple grain magnetic Fe in box3O4Structural unit, simple grain magnetic Fe3O4Structural unit is as schemed
Shown in 2.
Further, physicochemical property detection is carried out to obtained organic decoration Magnetic Bentonite (CTAB/MB) made above,
The physicochemical properties of the organic decoration Magnetic Bentonite are as follows: the interlamellar spacing of the organic decoration Magnetic Bentonite is 1.30-
1.67nm, aperture 6.09-6.98nm, Kong Rongwei 0.36-0.47cm3·g–1, preferable thermostabilization can be kept at 300-700 DEG C
Property；Saturation magnetization value is in 19.63-31.12emug-1, 5-10s can realize separation of solid and liquid under the action of an external magnetic field,
Slightly soluble in strong acid, highly basic.
Organic decoration Magnetic Bentonite (CTAB/MB) of the invention is applied to Congo red (CR) and acid scarlet (GR)
Adsorption.
The present invention is based on natural montmorillonite (RB), carried magnetic nano Fe3O4Particle and organic modifier cetyl
Trimethylammonium bromide (CTAB), the organic decoration Magnetic Bentonite (CTAB/MB) prepared has loose aperture structure, inside and outside
Surface is stretched, and have preferable removal effect to Congo red and acid scarlet, reason is: (1) surface RB is with a large amount of
OH-, and CTAB contains CTAB+Group, magnetic Nano Fe3O4Particle surface contains NH3 +And NH2 +And H+Equal groups, these groups
It is acted on by electrostatic attraction and being combined with RB, and be supported on the surface RB；In addition, CTAB belongs to quaternary ammonium salt, a large amount of methyl in surface
(CH3 +) and methine (CH2 +) Mg in group and RB2+、Ca2+Deng cation between certain complexing can occur, to make
CTAB is combined with RB；(2) cationicsurfactants are a kind of pore-foaming agents, during solid-liquid is combined to, CTAB
Between RB the generation of ion-exchange reactions and have part CTAB insertion RB layer edge, improve RB surface pore structure, because
And CTAB in conjunction with RB after can make the aperture increases of RB to a certain extent, form mesoporous material, improve adsorption capacity, favorably
In the absorption to Congo red (CR) and acid scarlet (GR)；(3) CR and GR belongs to anionic property dyestuff, under the acid condition of pole,
It can be in conjunction with the H of protonation+To form cation, the K in CTAB/MB+、Ca2+、Na+、Mg2+Pass through ion friendship Deng cation
It changes effect to swap with the cation in CR and GR, to generate suction-operated to CR and GR.
Natural montmorillonite used in the present invention (RB) are as follows: natural calcium-base bentonite original soil is purified, uses pulverizer after dry
The purifying bentonite that ground 200-400 mesh obtains.
Beneficial effects of the present invention:
(1) addition of cetyl trimethylammonium bromide, the hole for increasing natural montmorillonite holds aperture, to increase it
To the adsorption capacity of dyestuff；Magnetic Nano Fe3O4Particle can not only make CTAB and natural montmorillonite combine even closer, firm
Gu and can quickly make under the action of externally-applied magnetic field composite material realize be separated by solid-liquid separation, to recycle.Therefore,
Organic decoration Magnetic Bentonite (CTAB/MB) of the invention is not only strong to the adsorption capacity of anionic dye, realizes to the Congo
The high adsorption rate of red (CR) and acid scarlet (GR), and magnetic response ability and Magneto separate ability are strong, in the effect of externally-applied magnetic field
Under may be implemented to be separated by solid-liquid separation faster, easily recycling recycled.
(2) preparation process of the invention is easy, quick, and required raw material sources are wide, at low cost, is suitble to promote and apply.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of CTAB/MB of the invention；
Fig. 2 is simple grain magnetic Fe3O4Structural unit schematic diagram；
Fig. 3 is the process flow chart that the present invention prepares CTAB-MB；
Fig. 4 is the X ray diffracting spectrum of RB (a), MB (b) and CTAB/MB (c)；
Fig. 5 is the N of MB2Adsorption-desorption isothermal and its corresponding pore-size distribution situation；
Fig. 6 is the N of CTAB/MB2Adsorption-desorption isothermal and its corresponding pore-size distribution situation；
Fig. 7 is the FT-IR figure of MB and CTAB/MB；
Fig. 8 is the TGA figure of MB and CTAB/MB；
Fig. 9 is the DTA figure of MB and CTAB/MB；
Figure 10 is the VSM figure of MB and CTAB/MB；
Figure 11-12 is the TEM figure of CTAB/MB；
Figure 13 is influence result figure of the adsorption time to MB and CTAB/MB absorption CR and GR；
Figure 14 is influence result figure of the pH to MB and CTAB/MB absorption CR and GR；
Figure 15 is that MB and CTAB/MB absorption CR recycles experimental result picture；
Figure 16 is that MB and CTAB/MB absorption GR recycles experimental result picture.
Specific embodiment
Below in conjunction with specific embodiment and Figure of description, the present invention is described in more detail, but is not limited to the present invention
Protection scope.
Comparative example 1
The preparation of Magnetic Bentonite (referred to as: MB)
(1) by 0.3517g FeCl3·6H2O and 0.1393g FeCl2·4H2O, which is dissolved in 55ml deionized water, to be placed on
Microwave solid-liquid is combined in instrument and cooperates stirring, stirring rate 350rpmmin-1, microwave parameters are as follows: and 60 DEG C, 600W, mixing
Then 8mL ammonium hydroxide is added in phase (0), first microwave preheating 3min, then carry out microwave heating reaction 30min；Then ageing stirring
350min obtains Fe3O4Magnetic fluid；
(2) 2g natural montmorillonite is dissolved in 50ml deionized water, ultrasonic disperse and stirring 20min, obtains bentonite suspension
Liquid；
(3) Fe is added in bentonite suspension3O4In magnetic fluid, mixed liquor is obtained, then carries out microwave heating reaction 4h simultaneously
Cooperation stirring, stirring rate 350rpmmin-1, microwave parameters are as follows: 60 DEG C, 600W, mixed phase (0) cools down after reaction
It to room temperature, is then washed 3 times with dehydrated alcohol, then it is 7 that 3 pH to mixed liquor, which are washed with deionized, is filtered with the machine of suction filtration
To dehydration, then it is placed in a vacuum drying oven in 60 DEG C of vacuum drying 12h to get MB.
Prepare embodiment 1
A kind of preparation method of organic decoration Magnetic Bentonite (referred to as: CTAB/MB), this method are as follows: coprecipitated using microwave
Magnetic Nano Fe is prepared in shallow lake method3O4It is loaded on natural montmorillonite after particle, obtains Magnetic Bentonite, use hexadecane
Base trimethylammonium bromide is surface modified Magnetic Bentonite as organic modifier, and CTAB/MB can be obtained.It specifically includes
Following steps:
(1)Fe3O4The preparation of magnetic fluid: by 0.2164g FeCl3·6H2O and 0.0796g FeCl2·4H2O is completely dissolved
It is placed on microwave solid-liquid in 50mL deionized water and is combined in instrument and cooperates stirring, stirring rate 300rpmmin-1, micro-
Wave parameter are as follows: 60 DEG C, 600W, then 8mL ammonium hydroxide is added in mixed phase (0), first microwave preheating 3min, then to carry out microwave heating anti-
Answer 30min；Then ageing stirring 300min, obtains Fe3O4Magnetic fluid；
(2) 1g cetyl trimethylammonium bromide and 1g natural montmorillonite the preparation of mixed dispersion liquid: are dissolved in 50mL
In ionized water, ultrasonic disperse 10min obtains mixed dispersion liquid；
(3) Fe the preparation of organic decoration Magnetic Bentonite: is added in mixed dispersion liquid3O4In magnetic fluid, suspension is obtained,
Then it carries out microwave heating reaction 2h and cooperates stirring, stirring rate 300rpmmin-1, microwave parameters are as follows: and 60 DEG C, 600W,
Mixed phase (0), is cooled to room temperature after reaction, and then washing 3 pH to suspension with dehydrated alcohol is 8, with the machine of suction filtration
It filters to after being dehydrated, then is placed in a vacuum drying oven in 60 DEG C of vacuum drying 8h to get CTAB/MB.
Prepare embodiment 2
A kind of preparation method of organic decoration Magnetic Bentonite (referred to as: CTAB/MB), this method are as follows: coprecipitated using microwave
Magnetic Nano Fe is prepared in shallow lake method3O4It is loaded on natural montmorillonite after particle, obtains Magnetic Bentonite, use hexadecane
Base trimethylammonium bromide is surface modified Magnetic Bentonite as organic modifier, and organic decoration magnetism swelling can be obtained
Soil.
Specifically includes the following steps:
(1)Fe3O4The preparation of magnetic fluid: by 0.3787g FeCl3·6H2O and 0.1393g FeCl2·4H2O is completely dissolved
It is placed on microwave solid-liquid in 55mL deionized water and is combined in instrument and cooperates stirring, stirring rate 350rpmmin-1, micro-
Wave parameter are as follows: 60 DEG C, 600W, then 9mL ammonium hydroxide is added in mixed phase (0), first microwave preheating 3min, then to carry out microwave heating anti-
Answer 35min；Then ageing stirring 350min, obtains Fe3O4Magnetic fluid；
(2) 1g cetyl trimethylammonium bromide and 1g natural montmorillonite the preparation of mixed dispersion liquid: are dissolved in 50mL
In ionized water, ultrasonic disperse 20min obtains mixed dispersion liquid；
(3) Fe the preparation of organic decoration Magnetic Bentonite: is added in mixed dispersion liquid3O4In magnetic fluid, suspension is obtained,
Then it carries out microwave heating reaction 4h and cooperates stirring, stirring rate 350rpmmin-1, microwave parameters are as follows: and 60 DEG C, 600W,
Mixed phase (0), is cooled to room temperature after reaction, is then washed 3 times with dehydrated alcohol, then is washed with deionized 2 times and extremely hangs
The pH of supernatant liquid be 7, filtered with suction filtration machine to dehydration, then be placed in a vacuum drying oven in 60 DEG C of vacuum drying 11h to get
CTAB/MB。
Prepare embodiment 3
A kind of preparation method of organic decoration Magnetic Bentonite (referred to as: CTAB/MB), this method are as follows: coprecipitated using microwave
Magnetic Nano Fe is prepared in shallow lake method3O4It is loaded on natural montmorillonite after particle, obtains Magnetic Bentonite, use hexadecane
Base trimethylammonium bromide is surface modified Magnetic Bentonite as organic modifier, and organic decoration magnetism swelling can be obtained
Soil.
Specifically includes the following steps:
(1)Fe3O4The preparation of magnetic fluid: by 0.3517g FeCl3·6H2O and 0.1393g FeCl2·4H2O is completely dissolved
It is placed on microwave solid-liquid in 55mL deionized water and is combined in instrument and cooperates stirring, stirring rate 350rpmmin-1, micro-
Wave parameter are as follows: 60 DEG C, 600W, then 8mL ammonium hydroxide is added in mixed phase (0), first microwave preheating 4min, then to carry out microwave heating anti-
Answer 30min；Then ageing stirring 350min, obtains Fe3O4Magnetic fluid；
(2) 1g cetyl trimethylammonium bromide and 2g natural montmorillonite the preparation of mixed dispersion liquid: are dissolved in 50mL
In ionized water, ultrasonic disperse 20min obtains mixed dispersion liquid；
(3) Fe the preparation of organic decoration Magnetic Bentonite: is added in mixed dispersion liquid3O4In magnetic fluid, suspension is obtained,
Then it carries out microwave heating reaction 4h and cooperates stirring, stirring rate 350rpmmin-1, microwave parameters are as follows: and 60 DEG C, 600W,
Mixed phase (0), is cooled to room temperature after reaction, is then washed 3 times with dehydrated alcohol, then is washed with deionized 3 times and extremely hangs
The pH of supernatant liquid be 7, filtered with suction filtration machine to dehydration, then be placed in a vacuum drying oven in 60 DEG C of vacuum drying 12h to get
CTAB/MB。
Prepare embodiment 4
A kind of preparation method of organic decoration Magnetic Bentonite (referred to as: CTAB/MB), this method are as follows: coprecipitated using microwave
Magnetic Nano Fe is prepared in shallow lake method3O4It is loaded on natural montmorillonite after particle, obtains Magnetic Bentonite, use hexadecane
Base trimethylammonium bromide is surface modified Magnetic Bentonite as organic modifier, and organic decoration magnetism swelling can be obtained
Soil.
Specifically includes the following steps:
(1)Fe3O4The preparation of magnetic fluid: by 1.4066g FeCl3·6H2O and 0.5174g FeCl2·4H2O is completely dissolved
It is placed on microwave solid-liquid in 60mL deionized water and is combined in instrument and cooperates stirring, stirring rate 400rpmmin-1, micro-
Wave parameter are as follows: 60 DEG C, 600W, then 10mL ammonium hydroxide is added in mixed phase (0), first microwave preheating 5min, then to carry out microwave heating anti-
Answer 40min；Then ageing stirring 350min, obtains Fe3O4Magnetic fluid；
(2) 1g cetyl trimethylammonium bromide and 2g natural montmorillonite the preparation of mixed dispersion liquid: are dissolved in 60mL
In ionized water, ultrasonic disperse 20min obtains mixed dispersion liquid；
(3) Fe the preparation of organic decoration Magnetic Bentonite: is added in mixed dispersion liquid3O4In magnetic fluid, suspension is obtained,
Then it carries out microwave heating reaction 4h and cooperates stirring, stirring rate 400rpmmin-1, microwave parameters are as follows: and 60 DEG C, 600W,
Mixed phase (0), is cooled to room temperature after reaction, is then washed 2 times with dehydrated alcohol, then is washed with deionized 2 times and extremely hangs
The pH of supernatant liquid be 7.5, filtered with suction filtration machine to dehydration, then be placed in a vacuum drying oven in 60 DEG C of vacuum drying 10h to get
CTAB/MB。
Prepare embodiment 5
A kind of preparation method of organic decoration Magnetic Bentonite (referred to as: CTAB/MB), this method are as follows: coprecipitated using microwave
Magnetic Nano Fe is prepared in shallow lake method3O4It is loaded on natural montmorillonite after particle, obtains Magnetic Bentonite, use hexadecane
Base trimethylammonium bromide is surface modified Magnetic Bentonite as organic modifier, and organic decoration magnetism swelling can be obtained
Soil.
Specifically includes the following steps:
(1)Fe3O4The preparation of magnetic fluid: by 1.4066g FeCl3·6H2O and 0.6468g FeCl2·4H2O is completely dissolved
It is placed on microwave solid-liquid in 60mL deionized water and is combined in instrument and cooperates stirring, stirring rate 350rpmmin-1, micro-
Wave parameter are as follows: 60 DEG C, 600W, then 10mL ammonium hydroxide is added in mixed phase (0), first microwave preheating 5min, then to carry out microwave heating anti-
Answer 30min；Then ageing stirring 350min, obtains Fe3O4Magnetic fluid；
(2) 1g cetyl trimethylammonium bromide and 2g natural montmorillonite the preparation of mixed dispersion liquid: are dissolved in 60mL
In ionized water, ultrasonic disperse 10min obtains mixed dispersion liquid；
(3) Fe the preparation of organic decoration Magnetic Bentonite: is added in mixed dispersion liquid3O4In magnetic fluid, suspension is obtained,
Then it carries out microwave heating reaction 3h and cooperates stirring, stirring rate 450rpmmin-1, microwave parameters are as follows: and 60 DEG C, 600W,
Mixed phase (0), is cooled to room temperature after reaction, and then washing 3 pH to suspension with dehydrated alcohol is 8, with the machine of suction filtration
It filters to after being dehydrated, then is placed in a vacuum drying oven in 60 DEG C of vacuum drying 9h to get CTAB/MB.
Embodiment 6
To Congo red (CR) and acid scarlet (GR) adsorption experiment:
(1) influence of adsorption time: will prepare the CTAB/MB that embodiment 3 obtains and the MB that comparative example 1 obtains is distinguished
It is added in a series of conical flask of CR dye liquors equipped with 50mL 50mg/L and GR dye liquor, the dosage of adsorbent in CR dye liquor
For 0.4g/L, the dosage of adsorbent is 1.2g/L in GR dye liquor, is vibrated in thermostatic control oscillator vibration, and temperature is 25 DEG C,
A conical flask is taken out in 0-300min different time intervals, is surveyed in supernatant under 518nm and 580nm wavelength condition respectively
The absorbance of CR and GR dye liquor calculates the removal rate of dyestuff.
(2) influence of dye liquor initial pH value: the CR dye liquor that respectively takes 100mL 50mg/L, GR dye liquor are in the conical flask of 250mL
In, adjusting the pH of dye liquor with NaOH and HCl solution is 4-11, the adsorbent of 0.4g/L is added in CR dye liquor, in GR dye liquor
The adsorbent of 1.2g/L is added, oscillation 5h makes absorption reach balance, takes supernatant to measure dyestuff absorbance after centrifugation, calculate it and go
Except rate.
The material characterization of organic decoration Magnetic Bentonite
(1) phenetic analysis method
X-ray diffraction (X-Ray Diffraction, XRD) is to generate X when penetrating composite materials by its X-ray to penetrate
Line diffraction phenomena, to learn the crystal structure of composite materials, diffraction crystal face, crystal phase ingredient, characteristic peak and atom interlamellar spacing
Etc. relevant informations.The X-ray diffractometer that the present invention is produced using model D/max 2500V type Shimadzu Corporation, Japan is accurately surveyed
Examination, analysis sample object phase and structure, instrument tube voltage 40kV, tube current 20mA, 2 θ of scanning angle=5-80 °, scanning speed
10°/min。
Full-automatic specific surface and pore analysis instrument (Brunner-Emmet-Teller, BET) are characterize nano material one
Kind main method, for the specific surface area of analysis of material, pore volume and pore-size distribution etc..The present invention is swollen with original by composite material
The all data of profit soil compares, so as to clearly deduce the adsorption capacity of composite material.Needed before test to sample into
Row pretreatment: 100 DEG C of degassings in advance are no less than 6h to sample under vacuum conditions.
Fourier infrared spectrum (Fourier Transformed Infra-Red, FTIR), infrared spectrometer are with red
External spectrum is scanned specimen material, and functional group possessed by simultaneously COMPOSITE MATERIALS is detected by contrast standard card, from
And it can differentiate whether composite material is successfully prepared.The present invention matches the NicoletiS50 of Mo Feishier company using the U.S.
Type Fourier infrared spectrograph needs to pre-process sample before testing, add a small amount of KBr be ground into together with sample it is tiny
Transparent sheet is made in powdered granule, tabletting；Scanning angle is 4000-400cm–1。
Thermogravimetric analyzer (Thermogravimetric Analysis, TGA) is mainly used to analysis of material and temperature change
Relationship, to study its thermal stability and related component.DTG-60 (H) type that the present invention is produced using Japanese Shimadzu Co., Ltd
Thermogravimetric analyzer, needed before test setting instrument relevant parameter: 100 DEG C of initial temperature, 700 DEG C of final set temperature, heating rate
10°/min。
Vibrating specimen magnetometer (Vibrating Sample Magnetometer, VSM) is used to the magnetic saturation of test sample
Intensity and magnetic property.Of the present invention is 7410 type vibrating specimen magnetometers of U.S. lakeside company production, is needed before test
Instrument relevant parameter: test temperature 298K is set, and field scan range is -20000-20000Oe, step rate 6Oe/s.
Transmission electron microscope (Transmission Electron Microscope, TEM) is characterization nano material
Main method can get the important information of material morphology configuration aspects.It is super with soaked in absolute ethyl alcohol to laboratory sample material first
Sound 10-20min keeps sample fully dispersed, then drips to scattered sample in copper duplex support grid, and it is aobvious to be placed in transmitted electron
Observation analysis under micro mirror.
(2) (CTAB/MB that the MB and preparation embodiment 3 obtain to comparative example 1 is obtained is carried out phenetic analysis result
Phenetic analysis)
It is as shown in Figure 4 that 1.XRD analyzes result
Observed respectively in the XRD spectrum of MB and CTAB/MB montmorillonite in bentonite characteristic peak (2 θ=5.74 °,
19.80 °) and quartzy characteristic peak (2 θ=21.9 °), illustrate that organically-modified rear bentonitic basic structure is not destroyed.Positioned at 2
θ be 30.08 °, 35.41 °, 43.05 °, 56.94 ° and 62.52 ° at diffraction maximum, respectively with Fe3O4(220), (311),
(400), (511) are corresponding with (440) diffraction crystal face, illustrate Fe3O4It is successfully supported on MB and CTAB/MB.Due to Fe3O4
With the addition of CTAB, the montmorillonite of MB and CTAB/MB and the feature peak intensity of quartz are weaker than RB, Fe3O4Peak intensity be better than
RB.The interlamellar spacing d of RB, MB and CTAB/MB001Respectively 1.54nm, 1.30nm and 1.67nm, MB are reduced compared with RB interlamellar spacing
0.24nm, it may be possible to because of H during the preparation process+The Ca on RB is substituted2+, so as to cause the reduction of interlamellar spacing；And through CTAB
Modified, the interlamellar spacing of CTAB/MB slightly increases 0.13nm than RB, illustrates the long alkane in CTAB there is no being significantly significantly increased
Base does not enter into RB interlayer, is mainly attached to the surface RB, with Ca2+Ion exchange occurs, it may be possible to which part CTAB is inserted
The reason of entering one layer of hydrone of bentonite bed edge or bentonite adsorption, is increased slightly interlamellar spacing.
2.BET analyzes result as seen in figs. 5-6
Fig. 5 and Fig. 6 is respectively the N of MB and CTAB/MB2Adsorption-desorption isothermal and its corresponding pore-size distribution situation.From
Fig. 5 and Fig. 6 can be seen that the adsorption-desorption curve of MB and CTAB/MB in 0.44 < P/P0When < 0.97, adsorption-desorption isothermal
Ascendant trend it is gradually significant, at this time adsorption and desorption thermoisopleth separate, there is apparent lag regression phenomenon, belong to H3Type returns
Stagnant ring, this shows in the higher region of relative pressure, is not in absorption limitation.
It can also be seen that the thermoisopleth of MB and CTAB/MB belongs to IV type curve from Fig. 5 and Fig. 6, illustrate MB and CTAB/MB
Meso-hole structure is all had, and CTAB/MB ratio MB's is mesoporous more, the mesoporous absorption property for being conducive to improve material, therefore,
The absorption property of CTAB/MB is improved, and furthermore CTAB/MB magnetism is more stable, so being easier to carry out adsorption-desorption.
The specific surface area of MB and CTAB/MB and hole hold pore analysis the results are shown in Table 1, as shown in Table 1, CTAB/MB with
The MB average pore size that compares by 5.54nm increases to 6.98nm, and pore volume increases nearly 2 times, but specific surface area is by 86m2·g–1Subtract
As low as 74m2·g–1.The reason of wherein CTAB/MB specific surface area reduces may be that CTAB modifying agent is attached to the surface MB, with swelling
The Ca of soil2+Ion exchange occurs, and is covered on bentonite surface, so that the specific surface area of CTAB/MB be made to reduce；And its average hole
On the one hand the increase of diameter and pore volume is the ion-exchange reactions during being combined to due to solid-liquid, be on the other hand because
To there is part CTAB to be inserted into bentonitic layer edge, RB surface pore structure is improved.The increase of average pore size and pore volume
So that CTAB/MB has adsorption capacity more preferably than MB, it is more advantageous to the absorption to Congo red (CR) and acid scarlet (GR).
The specific surface area of table 1 MB and CTAB/MB and hole hold pore analysis result
| Material | BET specific surface area/m2·g–1 | Kong Rong/cm3·g–1 | Average pore size/nm |
| MB | 86 | 0.24 | 5.54 |
| CTAB/MB | 74 | 0.47 | 6.98 |
It is as shown in Figure 7 that 3.FT-IR analyzes result
As seen from Figure 7, MB is similar with the infrared spectroscopy peak shape of CTAB/MB, illustrate CTAB during modified MB,
The basic framework of RB is not destroyed.In 3620cm–1、1640cm–1And 1040cm–1Place corresponds respectively to bentonite structure water
Si-O-Si in hydroxyl-OH stretching vibration absworption peak, adsorbed water hydroxyl-OH bending vibration absorption peak and lattice stretches
Contracting vibration absorption peak.CTAB/MB increases 3 apparent characteristic peaks, respectively 2920cm compared to MB–1、2850cm–1With
1480cm–1The corresponding peak in wavelength place, wherein 2920cm–1And 2850cm–1Respectively correspond methyl-CH3With methine-CH2's
Stretching vibration peak, and 1480cm–1For methine-CH2Flexural vibrations peak.These all illustrate that MB successfully combines CTAB, are formed
CTAB/MB.
It is as shown in Figure 8 that 4.TGA analyzes result
From figure 8, it is seen that MB and CTAB/MB loses absorption water at 30-100 DEG C, intermediary water is lost at 100-400 DEG C,
Hydroxyl water is lost at 400-700 DEG C.Wherein the loss late of MB and CTAB/MB absorption water is respectively 2.5% and 3.1%, intermediary water
Loss late be respectively 1.6% and 3%, the loss late of hydroxyl water is respectively 3.4% and 2.1%, and total loss late is respectively
7.5% and 8.2%.
5.DTA result is as shown in Figure 9
From fig. 9, it can be seen that there are biggish weightless peaks at 77 DEG C for the DTA curve of MB, this is because MB absorption water damage
Caused by mistake；There are weightless peaks at 72 DEG C for the DTA curve of CTAB/MB, this is because caused by CTAB/MB absorption water loss.
During heated, the temperature that CTAB/MB loses absorption water is slightly less than the temperature that MB sloughs absorption water, but the final water damage of the two
Mistake rate is not much different, and illustrates that CTAB modification influences very little to the thermal stability of MB；And the two can keep tying in 30-700 DEG C
Structure is stablized, and illustrates that MB and CTAB/MB are able to maintain good thermal stability within this temperature range.
The results are shown in Figure 10 for 6.VSM analysis
As seen from Figure 10, the magnetic hysteresis regression curve of MB and CTAB/MB is " S " type hysteresis loop close to coincidence,
And the coercitive value of MB and CTAB/MB is respectively less than 5Oe and illustrates that two kinds of materials all have good superparamagnetic without hysteresis
Property.The saturation magnetic intensity of CTAB/MB is 31.12emug–1, 17.63emug higher than MB–1, this is mainly due to exposed
Nanometer Fe3O4Particle is easily oxidized in air, its magnetism is caused to weaken, and can be effectively prevented after CTAB organic decoration
Nanometer Fe3O4The effect that particle is oxidized because long-time is placed, therefore CTAB/MB ratio MB shows stronger Magneto separate ability,
It will quickly be directed and collect.In addition, when MB and CTAB/MB is in same externally-applied magnetic field, by the Magnetic Isolation of 5s,
Aqueous solution clarification, the separation that can be seen that CTAB/MB from the interior illustration in the lower right corner Figure 10 are thorough；By the Magnetic Isolation of 25s,
Can be seen that in the aqueous solution of MB from the interior illustration in the upper left corner Figure 10 still has a small amount of sample dispersion in bottom of bottle, and separation is not thorough.This
Illustrate that CTAB/MB is more conducive to be separated by solid-liquid separation, separating rate faster, more thoroughly, has more excellent magnetic response ability.
7.TEM analyzes result as depicted in figs. 11-12；
The pattern of layer structure is presented in CTAB/MB it can be seen from Figure 11-12, and has many reunite one on surface
The fine particle risen；Many studies demonstrate that the magnetic Fe that coprecipitation is prepared3O4Particle size is generally more than ten nanometers, shape
For it is irregular spherical and easily occur agglomeration, these illustrate Fe3O4Particle is successfully supported on bentonite.
From Figure 11-12 it can also be seen that the surface CTAB/MB other than having a large amount of fine particles, part bentonite surface with
And have at particle aggregation and condense into a piece of phenomenon, this is because CTAB is gradually covered on during preparing CTAB/MB
Caused by the surface of MB.
(3) to the Congo red and acid scarlet absorption property analysis (MB and preparation embodiment 3 obtained to comparative example 1
Obtained CTAB/MB carries out absorption property analysis)
1. influence of the adsorption time to MB and CTAB/MB absorption CR and GR is as shown in figure 13
As can be seen from Figure 13, as the removal rate curve of the increase of adsorption time, MB and CTAB/MB to CR and GR is all
The state that first rapid increase tends to balance again is presented.Absorption initial stage, the available absorption point in the surface MB and CTAB/MB compared with
It is more, therefore the rate of adsorption is larger, the removal rate of CR and GR quickly increase；With the progress of adsorption process, effectively adsorbs point and reduces,
Resistance of liquid mass transfer increases, and the rate of adsorption becomes smaller, finally tends to balance.Wherein, time of equilibrium adsorption of the MB and CTAB/MB to CR
Respectively 5h and 30min, adsorption equilibrium quantity at this time are respectively 75mg/L and 116mg/L；MB and CTAB/MB is flat to the absorption of GR
The weighing apparatus time is respectively 3h and 90min, and adsorption equilibrium quantity at this time is respectively 25mg/L and 59mg/L.As it can be seen that CTAB/MB to CR and
The adsorption rate and adsorption efficiency of GR is all much higher than MB, this is primarily due to CTAB as a kind of cationic surfactant, can
Bentonitic electropositive is remarkably reinforced, so that it more can be generated electrostatic attraction with anionic dye CR and GR, to improve it
Absorption property.
Influence of the 2.pH to MB and CTAB/MB absorption CR and GR is as shown in figure 14
It is seen from figure 14 that, with the increase of pH value, MB and CTAB/MB divide the removal rate of CR when pH value is 4-7
55% and 91% are not risen to by 18% and 87%, when pH value is 7-11, with the increase of pH value, MB and CTAB/MB are to CR
Removal rate 22% and 74% are reduced to by 55% and 91% respectively；And when pH value is 4-11, MB and CTAB/MB remove GR
Less except rate variation, stable 4% and 90% or so respectively.
Reason may be that CR and GR belong to anionic dyes, when pH value is 3-5, can protonate in binding soln
H+To form cation, with the Na in bentonite+、Ca2+Deng the cationic exchange interaction of generation, to realize MB and CTAB/
Absorption of the MB to CR and GR；When solution ph is 5-7, CR and GR dyestuff is easy to be ionized and negatively charged, and adsorbent surface is
With dyestuff electrostatic attraction effect occurs for positively charged cation；When pH value continues to increase to alkaline environment, CR and GR are in aqueous solution
In be easy to be ionized negatively charged (D-SO3 –), moreover, the increase of pH value can make the OH in water-Concentration increases, and adsorbent surface is born
Charge point increases and D-SO3 –Competitive Adsorption occurs, CTAB/MB is caused to decline the removal rate and adsorbance of CR and GR.
Either from adsorption time still from the point of view of the pH of dyestuff, CTAB/MB has preferably Congo red and acid scarlet
Adsorption effect, for MB, adsorption capacity has a distinct increment.
(4) interpretation of result (CTAB/MB that the MB and preparation embodiment 3 obtain to comparative example 1 is obtained is recycled
It carries out recycling performance evaluation)
1.MB and CTAB/MB absorption CR's and GR recycles experimental result as shown in figures 15-16
It can be seen from fig. 15 that testing by 5 adsorption-desorption cycles, MB drops to the adsorption rate of CR by 82%
61%, and CTAB/MB changes less the adsorption rate of CR, is held at 90% or more, each circulation absorption rate decline 3% is left
It is right.As can be seen from Figure 16, it being tested by 5 adsorption-desorption cycles, MB drops to 43% by 61% to the adsorption rate of GR, and
CTAB/MB changes less the adsorption rate of CR, is held at 90% or more, each circulation absorption rate decline 3% or so.
CTAB/MB shows performance more preferably than MB in terms of recycling, and makes it after being primarily due to CTAB modification MB
It adsorbs point to increase, absorption property is more preferable, and point is adsorbed after desorption can release again.Simultaneously as Fe3O4Machine maintenance is obtained
Decorations, magnetic core is more stable, and Magneto separate effect is more preferable, and catalyst loss is less in recycling, also conducive to the steady of adsorption efficiency
It is fixed.Therefore, CTAB/MB is a kind of adsorbent that can effectively reuse, and has good practical application potentiality.
Further, to preparation embodiment 1-2 and the preparation preparation-obtained organic decoration Magnetic Bentonite of embodiment 4-5
It carries out carrying out identical characterization with organic decoration Magnetic Bentonite prepared by preparation embodiment 3, all preparation embodiments are prepared into
To organic decoration Magnetic Bentonite characterization result be identical, illustrate that prepared product reproducibility is fabulous.
It is available according to the above analysis:
Structure determination is carried out to obtained organic decoration Magnetic Bentonite made above, which is
It is load matrix, carried magnetic nano Fe with natural montmorillonite3O4Particle, and with organic modifier cetyl trimethyl bromination
A kind of trielement composite material that ammonium is surface modified, structure are as shown in Figure 1；Sandwich-like object indicates natural montmorillonite in Fig. 1,
Substance is simple grain magnetic Fe in box3O4Structural unit, simple grain magnetic Fe3O4Structural unit is as shown in Figure 2.
Physicochemical property detection, the organic decoration magnetism swelling are carried out to obtained organic decoration Magnetic Bentonite made above
The physicochemical properties of soil are as follows: the interlamellar spacing of the organic decoration Magnetic Bentonite is 1.30-1.67nm, aperture 6.09-
6.98nm, Kong Rongwei 0.36-0.47cm3·g–1, preferable thermal stability can be kept at 300-700 DEG C；Saturation magnetization value
In 19.63-31.12emug-1, 5-10s can realize separation of solid and liquid under the action of an external magnetic field, the slightly soluble in strong acid, highly basic.
Organic decoration Magnetic Bentonite of the invention is applied to the Adsorption to Congo red (CR) and acid scarlet (GR).
Claims (10)
1. a kind of organic decoration Magnetic Bentonite, which is characterized in that the organic decoration Magnetic Bentonite is to be with natural montmorillonite
Load matrix, carried magnetic nano Fe3O4Particle, and be surface modified with organic modifier cetyl trimethylammonium bromide
A kind of trielement composite material, structure is as shown in Figure 1；Sandwich-like object indicates natural montmorillonite in Fig. 1, and substance is single in box
Grain magnetic Fe3O4Structural unit, simple grain magnetic Fe3O4Structural unit is as shown in Figure 2.
2. organic decoration Magnetic Bentonite according to claim 1, which is characterized in that the organic decoration Magnetic Bentonite
Interlamellar spacing be 1.30-1.67nm, aperture 6.09-6.98nm, Kong Rongwei 0.36-0.47cm3·g–1, can at 300-700 DEG C
Keep preferable thermal stability；Saturation magnetization value is in 19.63-31.12emug-1, 5-10s can under the action of an external magnetic field
It realizes and is separated by solid-liquid separation, the slightly soluble in strong acid, highly basic.
3. a kind of preparation method of organic decoration Magnetic Bentonite as claimed in claim 1 or 2, which is characterized in that this method
Are as follows: magnetic Nano Fe is prepared using microwave coprecipitation method3O4It is loaded on natural montmorillonite after particle, obtains magnetism
Bentonite is used cetyl trimethylammonium bromide to be surface modified as organic modifier to Magnetic Bentonite, be can be obtained
Organic decoration Magnetic Bentonite.
4. the preparation method of organic decoration Magnetic Bentonite according to claim 3, which is characterized in that the method is specific
The following steps are included:
(1)Fe3O4The preparation of magnetic fluid: by FeCl3·6H2O and FeCl2·4H2O dissolution completely after, first microwave preheating, then plus
Enter ammonium hydroxide, then carry out microwave heating reaction, then ageing stirring, obtains Fe3O4Magnetic fluid；
(2) preparation of mixed dispersion liquid: cetyl trimethylammonium bromide and natural montmorillonite is soluble in water, ultrasonic disperse,
Obtain mixed dispersion liquid；
(3) Fe the preparation of organic decoration Magnetic Bentonite: is added in mixed dispersion liquid3O4In magnetic fluid, suspension is obtained, then
Microwave heating reaction is carried out, is cooled to room temperature after reaction, being washed out to the pH of suspension is 7-8, then is dried in vacuo, i.e.,
Obtain organic decoration Magnetic Bentonite.
5. the preparation method of organic decoration Magnetic Bentonite according to claim 4, which is characterized in that the cetyl
The mass ratio of trimethylammonium bromide and natural montmorillonite is 1:1-1:2.
6. the preparation method of organic decoration Magnetic Bentonite according to claim 4, which is characterized in that the FeCl3·
6H2O and FeCl2·4H2The ratio between amount of substance of O is 1.6:1-2:1.
7. the preparation method of organic decoration Magnetic Bentonite according to claim 4, which is characterized in that the Fe3O4Magnetic current
Fe in body3O4Quality be cetyl trimethylammonium bromide and natural montmorillonite quality sum 5-20%.
8. the preparation method of organic decoration Magnetic Bentonite according to claim 4, which is characterized in that the microwave reaction
Shi Peihe stirring, stirring rate 300-450rpmmin-1；In the step (1), microwave reaction condition are as follows: microwave preheating rank
Section 3-5min, microwave heating stage 30-40min, microwave parameters are as follows: 60 DEG C, 600W, mixed phase (0)；It is micro- in the step (3)
Wave reaction condition are as follows: 2-4h, microwave parameters are reacted in microwave heating are as follows: 60 DEG C, 600W, mixed phase (0).
9. the preparation method of organic decoration Magnetic Bentonite according to claim 4, which is characterized in that the vacuum drying
Temperature be 60 DEG C, time 8-12h.
10. a kind of application of organic decoration Magnetic Bentonite as claimed in claim 1 or 2, which is characterized in that described to have machine maintenance
Magnetic Bentonite is adornd to be applied to Congo red and acid scarlet Adsorption.
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