CN106582561A - Preparation method and application of magnetic chitosan adsorption material - Google Patents
Preparation method and application of magnetic chitosan adsorption material Download PDFInfo
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- CN106582561A CN106582561A CN201710123394.3A CN201710123394A CN106582561A CN 106582561 A CN106582561 A CN 106582561A CN 201710123394 A CN201710123394 A CN 201710123394A CN 106582561 A CN106582561 A CN 106582561A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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Abstract
The invention discloses a preparation method of a magnetic chitosan adsorption material, and belongs to the technical field of composite material preparation. The preparation method comprises the following steps: a, dissolving chitosan in an aqueous FeCl3 solution, and magnetically stirring the chitosan and the aqueous FeCl3 solution to realize full mixing; b, adding ferroferric oxide nanoparticles, and mechanically stirring a solution obtained in step a and the ferroferric oxide nanoparticles to realize uniform mixing; c, pouring anhydrous ethanol to obtain a precipitate, filtering the obtained precipitate, and carrying out immersion cleaning on the precipitate with ethanol; d, carrying out vacuum drying on the precipitate obtained in step c, and grinding the dried precipitate to obtain magnetic powder; e, adding the magnetic powder obtained in step d to a glutaraldehyde-ethanol solution, and carrying out crosslinking; f, applying an external magnetic field after the crosslinking is completed in order to carry out separation, and cleaning obtained magnetic powder with deionized water; and g, carrying out vacuum drying on the cleaned magnetic powder obtained in step f to obtain the magnetic chitosan adsorption material. The magnetic chitosan adsorption material prepared in the invention has excellent adsorption ability to methyl orange, has good application to the pH, and has good regenerative performance.
Description
Technical field
The present invention relates to technical field of composite preparation, more particularly to a kind of preparation of chitosan magnetic sorbing material
Method and application.
Background technology
The features such as waste water from dyestuff has concentration height, color and luster depth, difficult degradation, complicated component, dyestuff is stable as a class formation
Organic compound, with antiacid alkali, it is anti-light, it is antimicrobial degraded etc. characteristic, can prolonged stay in the environment, have a strong impact on water
The normal function of body, destroys aquatic ecological environment.Using more azo dyes, anthraquinone dye, kiton colors etc. now
With certain carcinogenic mutagenesis characteristic, and its catabolite mostly is some carcinogenic aromatic compounds such as benzidine, enters
Entering also can be to human health and the immeasurable potential hazard of generation that grows of plant after water body.
Nowadays in order to remove water body in dyestuff reducing its impact to environment, it is proposed that multiple technologies, traditional skill
Art has adsorption bleaching, redox decolouring, coagulation decoloration etc., in addition, also ion exchange decolourized both at home and abroad, milipore filter decolourize and
Biological decolouring technology has carried out certain research.But for traditional coagulation decoloration processes waste water from dyestuff, resulting cost is higher,
And the high-concentration printing and dyeing wastewater special to some etc. is without treatment effect；Biological decolouring technology, one side waste water from dyestuff contains one
Determine toxicity, there is toxic action to microorganism, seriously suppress its existence growth, on the other hand because different biologies are to different dyes
Tolerance is also not quite similar, therefore also limit its application in dye wastewater treatment；Other processing methods, for example, aoxidize
Reducing process, ion-exchange, ultrafiltrationmembrane process etc. can play certain treatment effect, but operating cost is too high also to have impact on it
Application in practice.Therefore, for the various discoloration methods of dyeing waste water consider all from economy, technical and practicality
There is certain deficiency.
The features such as absorption method has simple to operate, low investment, high treating effect, has been a great concern.At present, mostly
Number waste water from dyestuff is decolourized using charcoal absorption.Activated carbon so that its unique loose structure, adsorption capacity be big, the rate of adsorption is fast,
In being widely used in wastewater treatment, but charcoal absorption has very strong selectivity, and price is high, and regeneration is difficult, no
The shortcomings of larger pollutional load can be born so as to which the application in terms of adsorption bleaching is restricted, is typically only applied to concentration
Relatively low treatment of dyeing wastewater or advanced treating.
Therefore, find cheap, efficient adsorbent come partly substitute activated carbon for waste water from dyestuff process, oneself becomes state
The hot research topic of inside and outside scholar.Recently, some metal corsslinking biomass polymers are held with its chemical stability and high absorption
Amount is attracted wide attention, and especially transition metal ions shows in the treatment of waste water huge with the complex of large biological molecule
Application prospect.
Publication No. CN 101973618A, publication date is that the Chinese patent literature of on 02 16th, 2011 discloses one kind
The method for being removed using shitosan-iron complex and reclaiming hexavalent chromium, including：(1) by shitosan monomer and iron ion
Mol ratio is 3-6：1 shitosan-iron complex is added to hexavalent chromium concentration for 10-200mg/L, the water that pH value is 3-10
In solution, stir at least 30 minutes, then filter Jing after centrifugation, the filter cake drying being filtrated to get obtains adsorbing hexavalent chromium ions
Shitosan-iron complex, described iron ion is ferric ion；(2) by the shitosan-iron complex of adsorbing hexavalent chromium ions
In being added to alkaline aqueous solution, stir at least 30 minutes, filter, the filtrate for obtaining is the recovery solution containing hexavalent chromium, institute
The alkaline aqueous solution stated is NaOH, Na2CO3Or NaHCO3The aqueous solution.
Shitosan-iron complex prepared by patent document pH value applicability during adsorption applications is poor；Absorption
After the completion of difficult separate, be not easy to reclaim；And do not carry out the regeneration tests of adsorbent, it is impossible to determine whether the material has and repeat profit
The property used.
The content of the invention
A kind of defect in order to overcome above-mentioned prior art of the invention, there is provided preparation method of chitosan magnetic sorbing material
And application, chitosan magnetic sorbing material prepared by the present invention, used as organic/inorganic composite material adsorbent, it has to methyl orange
There is excellent absorption property, the rate of adsorption is fast, adsorption capacity is big, insensitive to pH, applied widely；And can pass through additional magnetic
Field assembles it, easy separation of solid and liquid, and regenerability is good, can be used repeatedly, with preparation process is simple, low cost and ring
The characteristics of border is friendly.
The present invention is achieved through the following technical solutions：
A kind of preparation method of chitosan magnetic sorbing material, it is characterised in that comprise the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
In step a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 800-1600r/
Min, incorporation time is 4-6h.
In step a, deacetylation >=95% of shitosan.
In step b, the particle diameter of nano ferriferrous oxide granule is 200nm.
In step d, vacuum drying temperature is 80-95 DEG C.
In step e, crosslinking refers to and Magnaglo is added in glutaraldehyde ethanol solution, is placed in 30-35 DEG C of perseverance
2h is shaken with the speed of 180-200r/min in tepidarium concussion case.
The application of chitosan magnetic sorbing material, chitosan magnetic-iron sorbing material is added to containing 50-200mg/L
Methyl orange, during pH is for the waste water from dyestuff of 3-11, shakes 30min, and externally-applied magnetic field carries out separation of solid and liquid, obtains adsorbing the magnetic of methyl orange
Property shitosan-iron sorbing material, eliminates the methyl orange in waste water from dyestuff.
The regeneration of chitosan magnetic sorbing material, by the chitosan magnetic-iron sorbing material of absorption methyl orange alkali is added to
Property solution in, Magneto separate after concussion 30min obtains the recovered liquid containing methyl orange, then the chitosan magnetic after separation-iron is inhaled
Enclosure material is added in acid solution, activates 5-10min, then Jing Magneto separates, and drying obtains the chitosan magnetic-iron absorption for activating
Material.
The alkaline solution is the NaOH aqueous solution of 0.05mol/L.
The acid solution is the HCl/water solution of 0.1-0.5mol/L.
Beneficial effects of the present invention are mainly manifested in following aspect：
First, the present invention, a, is dissolved in FeCl by shitosan3In the aqueous solution, magnetic agitation is sufficiently mixed, and ensure that shitosan
Fully absorption Fe3+；B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed, and introduces magnetizing mediums so that postorder
The sorbing material of preparation is easy to reclaim；C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；d、
After by the sediment vacuum drying in step c, grinding obtains final product Magnaglo；E, the Magnaglo that step d is obtained is added to into penta
It is crosslinked in dialdehyde ethanol solution, the acid resistance of the sorbing material of postorder preparation can be strengthened, is easy to suitable under any environment
The property used；After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；G, finally will in step f clean
Rear Magnaglo is vacuum dried to obtain chitosan magnetic-iron sorbing material；By using magnetic obtained in a-g particular steps
Property shitosan sorbing material, used as organic/inorganic composite material adsorbent, it has excellent absorption property to methyl orange, absorption
Speed is fast, adsorption capacity is big, insensitive to pH, applied widely；And can assemble it by externally-applied magnetic field, easy solid-liquid point
It is good from, regenerability, can be used repeatedly, the characteristics of with preparation process is simple, low cost and environmental friendliness.
2nd, the present invention, in step a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 800-
1600r/min, incorporation time is 4-6h, FeCl3Amount is compared to shitosan excess so that shitosan further can fully adsorb
Fe3+；Magnetic agitation rotating speed is controlled in 800-1600r/min, is because that rotating speed is too small, shitosan and FeCl3Can not be fully contacted,
Cause shitosan to Fe3+Coordination is reduced, and affects the performance of sorbing material；Shitosan is long chain macromolecule, once rotating speed is too fast, pole
It is possible to interrupt shitosan chain, affects product quality, and causes the waste of resource；By experiment many times, finally give
Magnetic agitation rotating speed is specifically controlled in 800-1600r/min, the integrality of shitosan chain can either be ensured, shell can be made again
Glycan is sufficiently to Fe3+Coordination, has reached a good balance, and then ensure that the performance of final sorbing material；Mixing
Time is 4-6h, and the time, too short shitosan was to Fe3+Adsorption saturation can not be reached, overlong time then can cause in chitosan molecule
Protonated amino degree is deepened, and is affected to Fe3+Absorption property, specifically by incorporation time control in 4-6h, shell can be reduced
Protonated amino degree in glycan molecule, makes shitosan to Fe3+Fully absorption.
3rd, the present invention, in step a, deacetylation >=95% of shitosan, in the higher chitosan molecule of degree of deacetylation
Amino content is then bigger, and avtive spot is more, is more conducive to Fe3+Coordination.
4th, the present invention, in step b, the particle diameter of nano ferriferrous oxide granule is 200nm, is easy to and subsequent scans Electronic Speculum
Coordinated with transmission electron microscope, it is easy to observe.
5th, the present invention, in step d, vacuum drying temperature is 80-95 DEG C, using vacuum drying in dry run, can
Avoid and air contact, it is ensured that the final hydrolysate of iron is homogeneous, stable, specifically vacuum drying temperature is controlled in 80-95
DEG C, fully scattering and disappearing for moisture had both been can guarantee that in the short time, can also avoid the heat loss of organic matter.
6th, the present invention, in step e, crosslinking refers to and Magnaglo is added in glutaraldehyde ethanol solution, is placed in 30-35
DEG C water bath with thermostatic control concussion case in 2h is shaken with the speed of 180-200r/min, cross-linking reaction is the endothermic reaction, and temperature is higher anti-
Answer speed faster, and glutaraldehyde, ethanol are volatile substances, once temperature is too high, its rate of volatilization also can accordingly be accelerated, special
The crosslinking temperature scope of 30-35 DEG C of fixed employing slightly above room temperature, then can reach a balance well；It is specific to adopt
The speed concussion 2h of 180-200r/min, ensure that Magnaglo is well mixed with glutaraldehyde ethanol solution, it is ensured that crosslinking is anti-
The abundant generation answered.
7th, the present invention, chitosan magnetic-iron sorbing material is added to containing 50-200mg/L methyl oranges, and pH is 3-11
Waste water from dyestuff in, shake 30min, externally-applied magnetic field carries out separation of solid and liquid, obtains adsorbing chitosan magnetic-iron absorption of methyl orange
Material, eliminates the methyl orange in waste water from dyestuff, and chitosan magnetic-iron sorbing material has excellent adsorptivity to methyl orange
Can, the rate of adsorption is fast, adsorption capacity is big, insensitive to pH, applied widely.
8th, the present invention, the chitosan magnetic-iron sorbing material of absorption methyl orange is added in alkaline solution, is shaken
Magneto separate after 30min, obtains the recovered liquid containing methyl orange, then the chitosan magnetic after separation-iron sorbing material is added into acid
Property solution in, activate 5-10min, then Jing Magneto separates, drying obtains the chitosan magnetic-iron sorbing material for activating, by additional
Magnetic field assembles it, realizes good solid-liquid separation effect, and regenerability is good, can be used repeatedly, with preparation technology
Simply, low cost and the characteristics of environmental friendliness.
9th, the present invention, alkaline solution for 0.05mol/L the NaOH aqueous solution, from experimental data, with NaOH it is water-soluble
The increase of liquid concentration, desorption rate reduces on the contrary, and concentration is too small, does not reach desorption effect, specific using 0.05mol/L's
Concentration, can either ensure desorption effect, desorption rate can be improved again and is economized on resources.
Tenth, the present invention, acid solution is HCl/water solution, and the addition of HCl mainly neutralizes NaOH, activating activities site, from
And possessing adsorptivity again, the concentration of HCl/water solution adopts 0.1-0.5mol/L, both can guarantee that activation is complete, can guarantee that work again
The stability of absorption property after change, with good effect.
Description of the drawings
The present invention is described in further detail below in conjunction with specification drawings and specific embodiments, wherein：
Fig. 1 is the scanning electron microscope (SEM) photograph of chitosan magnetic of the present invention-iron sorbing material；
Fig. 2 is the transmission electron microscope picture of chitosan magnetic of the present invention-iron sorbing material.
Specific embodiment
Embodiment 1
A kind of preparation method of chitosan magnetic sorbing material, comprises the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed, and ensure that shitosan fully adsorbs Fe3 +；B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed, and introduces magnetizing mediums so that absorption prepared by postorder
Material is easy to reclaim；C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；D, by step c
After sediment vacuum drying, grinding obtains final product Magnaglo；E, that the Magnaglo that step d is obtained is added to into glutaraldehyde ethanol is molten
It is crosslinked in liquid, the acid resistance of the sorbing material of postorder preparation, the applicability being easy under any environment can be strengthened；F, crosslinking
After the completion of, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；G, finally by step f clean after magnetic powder
End is vacuum dried to obtain chitosan magnetic-iron sorbing material；By being inhaled using chitosan magnetic obtained in a-g particular steps
Enclosure material, used as organic/inorganic composite material adsorbent, it has excellent absorption property to methyl orange, and the rate of adsorption is fast, suction
Attached capacity is big, insensitive to pH, applied widely；And can assemble it by externally-applied magnetic field, and easy separation of solid and liquid, regenerability
Well, can be used repeatedly, the characteristics of with preparation process is simple, low cost and environmental friendliness.
Embodiment 2
A kind of preparation method of chitosan magnetic sorbing material, comprises the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
In step a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 800r/min, mixing
Time is 4h.
In step a, the deacetylation of shitosan is 95%.
In step b, the particle diameter of nano ferriferrous oxide granule is 200nm.
In step d, vacuum drying temperature is 80 DEG C.
In step e, crosslinking refers to and Magnaglo is added in glutaraldehyde ethanol solution, is placed in 30 DEG C of thermostatted water
2h is shaken with the speed of 180r/min in bath concussion case.
Embodiment 3
A kind of preparation method of chitosan magnetic sorbing material, comprises the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
In step a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 1200r/min, is mixed
The conjunction time is 5h.
In step a, the deacetylation of shitosan is 96%.
In step b, the particle diameter of nano ferriferrous oxide granule is 200nm.
In step d, vacuum drying temperature is 90 DEG C.
In step e, crosslinking refers to and Magnaglo is added in glutaraldehyde ethanol solution, is placed in 32 DEG C of thermostatted water
2h is shaken with the speed of 190r/min in bath concussion case.
The application of chitosan magnetic sorbing material, chitosan magnetic-iron sorbing material is added to containing 100mg/L methyl
Orange, pH is in 3 waste water from dyestuff, to shake 30min, and externally-applied magnetic field carries out separation of solid and liquid, and the magnetic crust for obtaining adsorbing methyl orange gathers
Sugar-iron sorbing material, eliminates the methyl orange in waste water from dyestuff.
Embodiment 4
A kind of preparation method of chitosan magnetic sorbing material, comprises the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
In step a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 1600r/min, is mixed
The conjunction time is 6h.
In step a, the deacetylation of shitosan is 97%.
In step b, the particle diameter of nano ferriferrous oxide granule is 200nm.
In step d, vacuum drying temperature is 95 DEG C.
In step e, crosslinking refers to and Magnaglo is added in glutaraldehyde ethanol solution, is placed in 35 DEG C of thermostatted water
2h is shaken with the speed of 200r/min in bath concussion case.
The application of chitosan magnetic sorbing material, chitosan magnetic-iron sorbing material is added to containing 150mg/L methyl
Orange, pH is in 5 waste water from dyestuff, to shake 30min, and externally-applied magnetic field carries out separation of solid and liquid, and the magnetic crust for obtaining adsorbing methyl orange gathers
Sugar-iron sorbing material, eliminates the methyl orange in waste water from dyestuff.
The regeneration of chitosan magnetic sorbing material, by the chitosan magnetic-iron sorbing material of absorption methyl orange alkali is added to
Property solution in, Magneto separate after concussion 30min obtains the recovered liquid containing methyl orange, then the chitosan magnetic after separation-iron is inhaled
Enclosure material is added in acid solution, activates 5min, then Jing Magneto separates, and drying obtains the chitosan magnetic-iron adsorption material for activating
Material.
Embodiment 5
A kind of preparation method of chitosan magnetic sorbing material, comprises the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
In step a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 1600r/min, is mixed
The conjunction time is 6h.
In step a, the deacetylation of shitosan is 97%.
In step b, the particle diameter of nano ferriferrous oxide granule is 200nm.
In step d, vacuum drying temperature is 95 DEG C.
In step e, crosslinking refers to and Magnaglo is added in glutaraldehyde ethanol solution, is placed in 35 DEG C of thermostatted water
2h is shaken with the speed of 200r/min in bath concussion case.
The application of chitosan magnetic sorbing material, chitosan magnetic-iron sorbing material is added to containing 200mg/L methyl
Orange, pH is in 9 waste water from dyestuff, to shake 30min, and externally-applied magnetic field carries out separation of solid and liquid, and the magnetic crust for obtaining adsorbing methyl orange gathers
Sugar-iron sorbing material, eliminates the methyl orange in waste water from dyestuff.
The regeneration of chitosan magnetic sorbing material, by the chitosan magnetic-iron sorbing material of absorption methyl orange alkali is added to
Property solution in, Magneto separate after concussion 30min obtains the recovered liquid containing methyl orange, then the chitosan magnetic after separation-iron is inhaled
Enclosure material is added in acid solution, activates 8min, then Jing Magneto separates, and drying obtains the chitosan magnetic-iron adsorption material for activating
Material.
Embodiment 6
A kind of preparation method of chitosan magnetic sorbing material, comprises the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
In step a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 1600r/min, is mixed
The conjunction time is 6h.
In step a, the deacetylation of shitosan is 97%.
In step b, the particle diameter of nano ferriferrous oxide granule is 200nm.
In step d, vacuum drying temperature is 95 DEG C.
In step e, crosslinking refers to and Magnaglo is added in glutaraldehyde ethanol solution, is placed in 35 DEG C of thermostatted water
2h is shaken with the speed of 200r/min in bath concussion case.
The application of chitosan magnetic sorbing material, chitosan magnetic-iron sorbing material is added to containing 200mg/L methyl
Orange, pH is in 11 waste water from dyestuff, to shake 30min, and externally-applied magnetic field carries out separation of solid and liquid, and the magnetic crust for obtaining adsorbing methyl orange gathers
Sugar-iron sorbing material, eliminates the methyl orange in waste water from dyestuff.
The regeneration of chitosan magnetic sorbing material, by the chitosan magnetic-iron sorbing material of absorption methyl orange alkali is added to
Property solution in, Magneto separate after concussion 30min obtains the recovered liquid containing methyl orange, then the chitosan magnetic after separation-iron is inhaled
Enclosure material is added in acid solution, activates 10min, then Jing Magneto separates, and drying obtains the chitosan magnetic-iron adsorption material for activating
Material.
The alkaline solution is the NaOH aqueous solution of 0.05mol/L.
The acid solution is the HCl/water solution of 0.1mol/L.
Embodiment 7
A kind of preparation method of chitosan magnetic sorbing material, comprises the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
In step a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 1600r/min, is mixed
The conjunction time is 6h.
In step a, the deacetylation of shitosan is 97%.
In step b, the particle diameter of nano ferriferrous oxide granule is 200nm.
In step d, vacuum drying temperature is 95 DEG C.
In step e, crosslinking refers to and Magnaglo is added in glutaraldehyde ethanol solution, is placed in 35 DEG C of thermostatted water
2h is shaken with the speed of 200r/min in bath concussion case.
The application of chitosan magnetic sorbing material, chitosan magnetic-iron sorbing material is added to containing 200mg/L methyl
Orange, pH is in 11 waste water from dyestuff, to shake 30min, and externally-applied magnetic field carries out separation of solid and liquid, and the magnetic crust for obtaining adsorbing methyl orange gathers
Sugar-iron sorbing material, eliminates the methyl orange in waste water from dyestuff.
The regeneration of chitosan magnetic sorbing material, by the chitosan magnetic-iron sorbing material of absorption methyl orange alkali is added to
Property solution in, Magneto separate after concussion 30min obtains the recovered liquid containing methyl orange, then the chitosan magnetic after separation-iron is inhaled
Enclosure material is added in acid solution, activates 10min, then Jing Magneto separates, and drying obtains the chitosan magnetic-iron adsorption material for activating
Material.
The alkaline solution is the NaOH aqueous solution of 0.05mol/L.
The acid solution is the HCl/water solution of 0.5mol/L.
In step b, the particle diameter of nano ferriferrous oxide granule is 200nm, is easy to and subsequent scans Electronic Speculum and transmission electron microscope
Coordinated, it is easy to observe.
Alkaline solution is the NaOH aqueous solution of 0.05mol/L, from experimental data, with the increasing of NaOH concentration of aqueous solution
Greatly, desorption rate reduces on the contrary, and concentration is too small, does not reach desorption effect, the specific concentration using 0.05mol/L, can either
Desorption effect is ensured, desorption rate can be improved again and is economized on resources.
Acid solution for 0.5mol/L HCl/water solution, the addition of HCl mainly neutralizes NaOH, activating activities site, from
And possessing adsorptivity again, the concentration of HCl/water solution adopts 0.5mol/L, both can guarantee that activation is complete, after activation is can guarantee that again
The stability of absorption property, with good effect.
The magnetic crust that cross-linked chitosan, shitosan-iron sorbing material are prepared with the present invention is gathered below by specific experiment
Sugar-iron sorbing material carries out adsorptivity comparative illustration：
Take the cross-linked chitosan of 0.03g, shitosan-iron sorbing material, chitosan magnetic-iron sorbing material respectively to be added to
50mL initial concentrations are respectively in the methyl orange solution of 50mg/L, 100mg/L, 200mg/L, room temperature concussion under 150r/min
30min, by chitosan magnetic-iron sorbing material Magneto separate, after cross-linked chitosan and shitosan-iron sorbing material centrifugation,
Methyl orange concentration in solution is determined using visible spectrophotometry, column table 1 is seen.
Cross-linked chitosan：CS
Shitosan-iron sorbing material：CS-Fe(Ⅲ)
Chitosan magnetic-iron sorbing material：Magnetic CS-Fe (III)
Column table 1
From column table 1, the removal efficiency of shitosan-iron sorbing material, chitosan magnetic-iron sorbing material, methyl
Orange concentration accommodation is wider, and clearance is up to more than 99% between 50-200mg/L, and shitosan effect is then far short of what is expected,
And the addition of nano ferriferrous oxide on its adsorption effect substantially without impact.
Chitosan magnetic-iron sorbing material pH adaptability is tested：
Chitosan magnetic-iron the sorbing material of 0.03g is taken, 50mL initial concentrations is added to for 200mg/L, pH is respectively 3,
5th, in 7,9,11 methyl orange solution, room temperature concussion 30min, Magneto separate, are determined using visible spectrophotometry under 150r/min
Methyl orange concentration in solution, is shown in column table 2.
Column table 2
From column table 2, using chitosan magnetic-iron sorbing material, under acid, alkalescence condition, to methyl orange
Adsorption rate reachable more than 97%, with good pH adaptability.
Chitosan magnetic-iron sorbing material is tested to the adsorption capacity of methyl orange：
Take the chitosan magnetic-iron sorbing material of 0.03g, be added to 50mL initial concentrations be respectively 50,100,200,
300th, 400,600,800,1000,1200,1600, in the methyl orange solution of 2000mg/L, room temperature is shaken to suction under 150r/min
Attached balance, Magneto separate determines methyl orange concentration in solution using visible spectrophotometry, is fitted Langmuir and Freundlich
Adsorption isotherm obtains fitting parameter, is shown in Table 3.
Table 3
As shown in Table 3, chitosan magnetic-iron sorbing material is 1149.42mg/g to the adsorption capacity of methyl orange, it is seen that inhaled
Attached capacity is big.
Chitosan magnetic-iron sorbing material is tested to the desorption rate of methyl orange：
Chitosan magnetic-iron the sorbing material of 0.03g is taken, the methyl orange that 50mL initial concentrations are 200mg/L is added to molten
In liquid, room temperature concussion 30min, after Magneto separate, obtains having adsorbed the chitosan magnetic-iron adsorption material of methyl orange under 150r/min
Material, be then separately added into again 50mL concentration be 0.05,0.1, the NaOH aqueous solution of 0.2mol/L, room temperature concussion under 150r/min
30min, is desorbed the methyl orange of absorption, is desorbed result, is shown in Table 4.
| Desorption conditions | Methyl orange desorption rate (%) |
| 0.05mol/L NaOH | 91.87 |
| 0.1mol/L NaOH | 89.52 |
| 0.2mol/L NaOH | 75.68 |
Table 4
As shown in Table 4,0.05mol/L NaOH are specifically adopted, had both can guarantee that methyl orange desorption rate, economized on resources again.
The regeneration tests of chitosan magnetic-iron sorbing material：
The NaOH water of 50mL0.05mol/L is separately added into in the chitosan magnetic-iron sorbing material for having adsorbed methyl orange
In solution, room temperature concussion 30min under 150r/min, the chitosan magnetic after being desorbed-iron sorbing material adds 25mL dense
The HCl/water solution for 0.1mol/L is spent, 10min is activated, after Magneto separate, drying obtains the chitosan magnetic-iron adsorption material for activating
Material, is finally added to the methyl orange solution that 50mL initial concentrations are 200mg/L by the chitosan magnetic of activation-iron sorbing material
In, room temperature concussion 30min, Magneto separate, determine methyl orange concentration in solution, as a result using visible spectrophotometry under 150r/min
It is shown in Table 5.
| Cycle-index | Adsorption rate (%) | Desorption rate (%) |
| 1 | 99.49 | 94.23 |
| 2 | 98.84 | 90.86 |
| 3 | 95.37 | 90.49 |
| 4 | 94.17 | 88.94 |
| 5 | 95.49 | 87.14 |
Table 5
As shown in Table 5, chitosan magnetic-iron sorbing material assembles it by externally-applied magnetic field, easy separation of solid and liquid, reproducibility
Can be good, can be used repeatedly.
By the scanning electron microscope (SEM) photograph and transmission electron microscope picture of chitosan magnetic-iron sorbing material, it is known that：
Chitosan magnetic-iron sorbing material ESEM is shown as with transmission electron microscope：Surface is in smooth random stratiform knot
Structure, non-porous structure, top layer is distributed with substantial amounts of particulate matter, these particle sizes can be observed by transmission electron microscope and is about
200nm is suitable with the nano ferriferrous oxide granule particle diameter for mixing, it was demonstrated that to introduce magnetic success.Therefore, chitosan magnetic-iron
Sorbing material is in application process, it is only necessary to externally-applied magnetic field, just can be reclaimed, and reclaims convenient, and does not affect its absorption property.
Claims (10)
1. a kind of preparation method of chitosan magnetic sorbing material, it is characterised in that comprise the following steps：
A, shitosan is dissolved in into FeCl3In the aqueous solution, magnetic agitation is sufficiently mixed；
B, incorporation nano ferriferrous oxide granule, mechanical agitation is allowed to be well mixed；
C, be subsequently poured into absolute ethyl alcohol separate out precipitation, after filtration, with ethanol sediment is embathed；
D, by step c sediment vacuum drying after, grinding, obtain final product Magnaglo；
E, the Magnaglo that step d is obtained is added in glutaraldehyde ethanol solution it is crosslinked；
After the completion of f, crosslinking, externally-applied magnetic field is separated, deionized water cleaning Magnaglo；
G, finally the Magnaglo after cleaning in step f vacuum dried obtained final product into chitosan magnetic-iron sorbing material.
2. the preparation method of a kind of chitosan magnetic sorbing material according to claim 1, it is characterised in that：The step
In a, FeCl3Consumption more than shitosan consumption, the rotating speed of magnetic agitation is 800-1600r/min, and incorporation time is 4-6h.
3. the preparation method of a kind of chitosan magnetic sorbing material according to claim 1, it is characterised in that：The step
In a, deacetylation >=95% of shitosan.
4. the preparation method of a kind of chitosan magnetic sorbing material according to claim 1, it is characterised in that：The step
In b, the particle diameter of nano ferriferrous oxide granule is 200nm.
5. the preparation method of a kind of chitosan magnetic sorbing material according to claim 1, it is characterised in that：The step
In d, vacuum drying temperature is 80-95 DEG C.
6. the preparation method of a kind of chitosan magnetic sorbing material according to claim 1, it is characterised in that：The step
In e, crosslinking refers to Magnaglo is added in glutaraldehyde ethanol solution, be placed in 30-35 DEG C of water bath with thermostatic control concussion case with
The speed concussion 2h of 180-200r/min.
7. the application of a kind of chitosan magnetic sorbing material according to claim 1, it is characterised in that：Magnetic crust is gathered
Sugar-iron sorbing material is added to containing 50-200mg/L methyl oranges, during pH is for the waste water from dyestuff of 3-11, shakes 30min, additional magnetic
Field carries out separation of solid and liquid, obtains adsorbing the chitosan magnetic-iron sorbing material of methyl orange, eliminates the methyl in waste water from dyestuff
Orange.
8. the regeneration of a kind of chitosan magnetic sorbing material according to claim 1, it is characterised in that：Methyl orange will be adsorbed
Chitosan magnetic-iron sorbing material be added in alkaline solution, concussion 30min after Magneto separate, obtain containing methyl orange return
Liquid is received, then the chitosan magnetic after separation-iron sorbing material is added in acid solution, activate 5-10min, then Jing Magneto separates,
Drying, obtains the chitosan magnetic-iron sorbing material for activating.
9. the regeneration of a kind of chitosan magnetic sorbing material according to claim 8, it is characterised in that：The alkaline solution
For the NaOH aqueous solution of 0.05mol/L.
10. the regeneration of a kind of chitosan magnetic sorbing material according to claim 8, it is characterised in that：The acidity is molten
Liquid is the HCl/water solution of 0.1-0.5mol/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107684904A (en) * | 2017-10-27 | 2018-02-13 | 成都理工大学 | A kind of chitose magnetic fluid water quality purification material, preparation method and applications |
| CN108355621A (en) * | 2018-03-21 | 2018-08-03 | 成都理工大学 | A kind of magnetic porous bentonite chitosan compound microsphere and preparation method thereof |
| CN109046268A (en) * | 2018-08-28 | 2018-12-21 | 武汉霖泉环保科技有限公司 | A kind of sewage treatment multifunctional ceiling enclosure material and preparation method thereof |
| CN110354815A (en) * | 2019-03-13 | 2019-10-22 | 广西中连智浩科技有限公司 | A kind of preparation method of graft modification chitosan magnetic flocculant |
| CN116618025A (en) * | 2023-05-25 | 2023-08-22 | 南京工业大学 | Novel bio-based adsorbent for selectively adsorbing anionic dye |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566906A (en) * | 2013-11-05 | 2014-02-12 | 河海大学 | Magnetic chitosan nanoparticle adsorbent, and preparation method and application thereof |
-
2017
- 2017-03-03 CN CN201710123394.3A patent/CN106582561A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566906A (en) * | 2013-11-05 | 2014-02-12 | 河海大学 | Magnetic chitosan nanoparticle adsorbent, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHENSI SHEN ET AL.: "Fast and highly efficient removal of dyes under alkaline conditions using magnetic chitosan-Fe(III) hydrogel", 《WATER RESEARCH》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107684904A (en) * | 2017-10-27 | 2018-02-13 | 成都理工大学 | A kind of chitose magnetic fluid water quality purification material, preparation method and applications |
| CN108355621A (en) * | 2018-03-21 | 2018-08-03 | 成都理工大学 | A kind of magnetic porous bentonite chitosan compound microsphere and preparation method thereof |
| CN108355621B (en) * | 2018-03-21 | 2022-04-01 | 成都理工大学 | Magnetic porous bentonite chitosan composite microsphere and preparation method thereof |
| CN109046268A (en) * | 2018-08-28 | 2018-12-21 | 武汉霖泉环保科技有限公司 | A kind of sewage treatment multifunctional ceiling enclosure material and preparation method thereof |
| CN109046268B (en) * | 2018-08-28 | 2022-02-11 | 武汉霖泉环保科技有限公司 | Multifunctional adsorption material for sewage treatment and preparation method thereof |
| CN110354815A (en) * | 2019-03-13 | 2019-10-22 | 广西中连智浩科技有限公司 | A kind of preparation method of graft modification chitosan magnetic flocculant |
| CN116618025A (en) * | 2023-05-25 | 2023-08-22 | 南京工业大学 | Novel bio-based adsorbent for selectively adsorbing anionic dye |
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