CN109876781A - A kind of preparation method and application of graft type chitosan magnetic micro-sphere - Google Patents
A kind of preparation method and application of graft type chitosan magnetic micro-sphere Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of graft type chitosan magnetic micro-sphere.The preparation method is that: pass through Co deposited synthesis CoFe2O4Nano particle；Again by reversed emulsion polymerization, under the crosslinked action of glutaraldehyde, by chitosan and CoFe2O4Nano particle is cross-linked into magnetic microsphere, is finally grafted using itaconic acid and acrylic acid to magnetic microsphere shell, obtains graft type chitosan magnetic micro-sphere.Invention additionally discloses be used to remove Th in waste water for graft type chitosan magnetic micro-sphere4+Application.Graft type chitosan magnetic micro-sphere prepared by the present invention is under acidic environment to Th in waste water4+Adsorption capacity it is big, to the Th in waste water4+Removal ability it is preferable；And can be separated from waste water quickly after absorption, it is Th in waste water4+Removal provide new approach.
Description
Technical field
The present invention relates to water-treatment technology fields, and in particular to a kind of preparation method of graft type chitosan magnetic micro-sphere and
Using.
Background technique
Thorium is common in the liquid radioactive wastes generated in core operation, radioactive isotope production and mining process puts
One of penetrating property element.Thorium element has radioactivity and toxicity also can be right even if low percentage Th (IV) ion contained in water source
Life system causes various adverse effects.Accordingly, it is considered to thorium extensive use in the industry and its in the environment long-term
Stability and its potential damage to human health and environment remove and recycle thorium ion from waste water and be necessary.It is various
Method has been used for recycling thorium ion from the waste containing this ion.Common processing method includes solvent extraction, chemistry
Precipitating, ion exchange, evaporation, biological adsorption etc..In above-mentioned processing method, absorption method is that removing heavy metals are removed from aqueous solution most
One of common method, its main feature is that it is high-efficient, at low cost, be easy to restore and environmental protection.
Currently used adsorbent mainly active charcoal and ion exchange resin.But active carbon does not have absorption selection
Property, and the higher cost of active carbon itself, therefore the use of active carbon is restricted.Active carbon after processing sewage needs to regenerate
It can just continue to use afterwards.The regeneration of active carbon not only increases use cost, also results in carbon loss to reduce adsorption capacity.
And ion exchange resin is a kind of expensive sorbent refined by petroleum, and water poor contact, and absorption property takes
Certainly in resin property.
Chitosan is one of biological adsorption agent abundant in nature as a kind of natural polymers.With other
Biopolymer is compared, and chitosan has huge adsorption capacity and potentiality, and there are amidos, hydroxyl isoreactivity function in structure
Group.But natural chitosan is readily soluble under acidic environment, and is difficult to separate from waste water after absorption, these disadvantages make
The application of chitosan is extremely limited.
Therefore, how chitosan is modified, it can be played and adsorb potential and reduce absorption cost, be this
The research direction of field technical staff.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of graft type chitosan magnetic is micro-
The preparation method of ball, the graft type chitosan magnetic micro-sphere prepared by this method can be used in handling the Th in waste water4+, and
Adsorption capacity is big, and removal ability is preferable.
Realize above-mentioned purpose, the present invention adopts the following technical scheme:
A kind of preparation method of graft type chitosan magnetic micro-sphere, passes through Co deposited synthesis CoFe2O4Nano particle；Again
By reversed emulsion polymerization, under the crosslinked action of glutaraldehyde, by chitosan and CoFe2O4Nano particle is cross-linked into magnetic micro-
Ball is finally grafted magnetic microsphere shell using itaconic acid and acrylic acid, obtains graft type chitosan magnetic micro-sphere.
Further, specific steps are as follows:
(1) by FeCl3·6H2O and CoCl2·6H2O is dissolved in the ethylene glycol solution containing ammonium acetate, and stirring is until completely molten
Solution, is then transferred in reaction kettle, and reaction kettle is placed in 180 DEG C of baking oven, and after heating reaction 20~24 hours, it is heavy to isolate
Starch, after being washed with deionized water and dehydrated alcohol, frozen drying for 24 hours, obtains particle dispersion and uniform CoFe2O4It receives
Rice grain；
(2) chitosan is taken to be dissolved in the acetic acid solution that percentage by volume is 2%, it, will be in step (1) after stirring 6~12h
CoFe2O4Nano particle is added in above-mentioned solution, stirs 5~10h, obtains mixed solution；By hexamethylene and Span 80 in three necks
1~2h is stirred in flask at 25 DEG C, the mixed solution is added, 3~6h is stirred, is warming up to 50 DEG C, adds mass fraction
For 50% glutaraldehyde, 1h is stirred；Sediment is successively used ethyl alcohol, distillation water washing, 10~12h of frozen drying to get
To chitosan magnetic micro-sphere；
(3) it disperses the chitosan magnetic micro-sphere that step (2) obtain in the three-neck flask equipped with ultrapure water, leads to
N230min removes oxygen in water, ammonium persulfate and sodium hydrogensulfite is added, in N2It is stirred 10 minutes under atmosphere, 0.1g/ is added
The itaconic acid solution and acrylic acid of mL, in 60 DEG C and N2After reacting 3~5h under atmosphere, sample is isolated with magnet, uses ultrapure water
Repeatedly washing, and 10~12h of frozen drying to get arrive graft type chitosan magnetic micro-sphere.
Wherein, in the step (1), FeCl3·6H2O and CoCl2·6H2The molar ratio of O is 2~2.5:1, the acetic acid
The mass volume ratio of ammonium and ethylene glycol solution is 1.16~2.32g:25~50mL.
In the step (1), reaction kettle is the stainless steel high-pressure hydrothermal reaction kettle of polytetrafluoroethyllining lining.
In the step (2), the volume for the acetic acid solution that volume fraction is 2% and the mass ratio of chitosan be 40~
50mL:1g；The CoFe2O4The mass ratio of nano particle and chitosan is 1:1.5~1.6；The volume ratio of hexamethylene and Span 80
For 100~200:0.7~1.3；The volume of glutaraldehyde and 0.6~0.7ml:1g of mass ratio of chitosan.
In the step (3), the ratio of chitosan magnetic micro-sphere and ultrapure water is 0.8~1.6g:75~150mL；Sulfurous
The molar ratio of 0.7~0.75:1 of mass ratio of sour hydrogen sodium and ammonium persulfate, ammonium persulfate and chitosan is 0.5~0.6:1, and shell is poly-
The mass ratio of sugar, itaconic acid and acrylic acid is 1:1.5~1.6:7~8.
Graft type chitosan magnetic micro-sphere is used to remove Th in waste water invention additionally discloses a kind of4+Application.
Wherein, the removal is the lower progress that is 0~5.0 in pH value.
Compared with prior art, the invention has the following beneficial effects:
1, graft type chitosan magnetic micro-sphere prepared by the present invention, due on the polymer of graft type chitosan magnetic micro-sphere
Functional groups amino, carboxyl and carbon-carbon double bond containing polycation, therefore absorption point is more, introduces especially by graft copolymerization
The copolymer of itaconic acid containing a large amount of carboxyl functional groups and acrylic acid since the oxygen of carboxyl has non-bonding electrons can be with gold
The unoccupied orbital cooperation for belonging to ion, forms coordinate bond absorption, a Th4+Ion and multiple electron carboxyl groups are coordinated, and formation has
The chelate of cyclic structure.Additionally, due to Th4+It can also be adsorbed by chelation with unreacted amine groups.Moreover, this
Invention enables natural chitosan to use under acidic environment and has good machine by being cross-linked into magnetic microsphere processing
Tool performance can be used in the Th under acidic environment4+Absorption, and adsorption capacity is big, to the Th in waste water4+Removal ability compared with
It is good, it is Th in waste water4+Removal provide new approach.
2, preparation process provided by the invention and easy to operate, it is with short production cycle, with EDTA fast desorption, product recovery rate
It is high.Adsorption capacity of graft type chitosan magnetic micro-sphere is 2.525mmol/g, and adsorption capacity is after primary recycling
2.437mmol/g, desorption rate are as follows: 96.5%；Adsorption capacity is 2.391mmol/g, desorption rate are as follows: 94.7% after secondary recycling；
Adsorption capacity is 2.331mmol/g, desorption rate after tertiary recycling are as follows: 92.3%, therefore can be realized multiple utilization, and then reduce
Processing cost.It is recycled using the magnetic responsiveness of graft type chitosan magnetic micro-sphere, recycling is quickly and cost recovery is low, is not required to
Want special chemical industry equipment, it is easy to accomplish industrialized production.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of chitosan magnetic micro-sphere prepared by embodiment 1 and graft type chitosan magnetic micro-sphere,
In: CS/CoFe2O4- IA-AA is graft type chitosan magnetic micro-sphere, CS/CoFe2O4For chitosan magnetic micro-sphere.
Fig. 2 is the CoFe for implementing to prepare in 12O4Nano particle, chitosan magnetic micro-sphere, graft type chitosan magnetic micro-sphere
XRD diagram, wherein CS/CoFe2O4- IA-AA is graft type chitosan magnetic micro-sphere, CS/CoFe2O4It is micro- for chitosan magnetic
Ball, CoFe2O4For CoFe2O4Nano particle.
Fig. 3 is the N of graft type chitosan magnetic micro-sphere2Adsorption-desorption isothermal.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
One, the preparation of graft type chitosan magnetic micro-sphere
Embodiment 1:
(1) by 0.54g FeCl3·6H2O and 0.24g CoCl2·6H2O is dissolved in the 25mL ethylene glycol of the ammonium acetate containing 1.16g
In solution, stir until being completely dissolved.Then the stainless steel high pressure hydro-thermal of the polytetrafluoroethyllining lining of 50mL is transferred the solution into
In reaction kettle, reaction kettle is placed in the baking oven for being previously heated to 180 DEG C, heating reaction 24 hours.After the reaction was completed, with magnetic point
From or be collected by centrifugation sediment, washed with deionized water and dehydrated alcohol and remove unreacted reactant and by-product, low temperature cold
Be lyophilized it is dry for 24 hours, obtain particle dispersion and uniform CoFe2O4Nano particle.
(2) it takes 1.6g chitosan to be dissolved in the acetic acid solution that percentage by volume is 2%80mL, 6~12h is stirred, by 1.6g
CoFe2O4Nano particle is added in above-mentioned solution, stirs 5~10h, until solution is in the sliding state of silk.By 200mL hexamethylene and 1.3mL
Span 80 stirs 1~2h in three-neck flask at 25 DEG C, then by chitosan CoFe2O4Mixed liquor is added, and stirs 3~6h, is warming up to
50 DEG C, 1mL50% glutaraldehyde is added, stirs 1h.Sediment is successively used to ethyl alcohol, distills water washing, frozen drying 10~
12h to get arrive chitosan magnetic micro-sphere.
(3) it disperses 1.6g chitosan magnetic micro-sphere in the three-neck flask equipped with 150mL ultrapure water, leads to N230min is gone
Except oxygen in water, 0.28g ammonium persulfate and 0.2g sodium hydrogensulfite is added, in N2It is stirred 10 minutes under atmosphere, 25mL is added
The itaconic acid solution and 11.44mL acrylic acid of 0.1g/mL, in 60 DEG C, N23~5h is reacted under atmosphere.It is isolated with magnet obtained
Sample, it is multiple with milli-Q water, 10~12h of frozen drying to get arrive graft type chitosan magnetic micro-sphere.
Step (2) preparation chitosan magnetic micro-sphere and step (3) preparation graft type chitosan magnetic micro-sphere it is infrared
Spectrogram is as shown in Figure 1, as we know from the figure: chitosan magnetic micro-sphere is in 1637cm-1Absorption peak it is corresponding be amido and penta 2
The C=N group that the aldehyde radical of aldehyde is formed by schiff base reaction.Graft type chitosan magnetic micro-sphere is in 1718cm-1Absorption peak is corresponding
Be caused by the vibration of C=O group, in addition in 1640cm-1Nearby without apparent absorption peak, illustrate corresponding C=C and N-
H group all reacts, therefore illustrates that acrylic acid and itaconic acid have successfully been grafted on chitosan magnetic micro-sphere.
Fig. 2 is the CoFe for implementing to prepare in 12O4Nano particle, chitosan magnetic micro-sphere, graft type chitosan magnetic micro-sphere
XRD diagram.CoFe2O4Five main feature diffraction maximums appear at 30.06,35.45,43.47,57.16 and 62.72, they
It is marked respectively with corresponding index (220), (311), (400), (511) and (440).In chitosan magnetic micro-sphere and graft type magnetic
On the diffracting spectrum of property chitosan microball, it is able to observe that CoFe2O4Characteristic diffraction peak, illustrate in chitosan magnetic micro-sphere
CoFe is not destroyed in synthesis and grafting process2O4Crystal structure, therefore, step (2) preparation chitosan magnetic micro-sphere and step
Suddenly the graft type chitosan magnetic micro-sphere of (3) preparation all has magnetism, can realize separation and recycling by magnetic.
The N of graft type chitosan magnetic micro-sphere2Adsorption-desorption isothermal is as shown in Figure 3.Pass through N2- physical absorption (BET)
The specific surface area of the available magnetic material is 5.7520m2/g.From the figure 3, it may be seen that hysteretic loop (H1 type) corresponds to IV type isothermal
Line, high porosity, column pore structure show to exist simultaneously column mesoporous structure in graft type chitosan magnetic micro-sphere.It is porous logical
Road plays a crucial role the diffusion of substance in adsorption process.Therefore, opening in graft type chitosan magnetic micro-sphere
Pore structure and high porosity can promote Th4+Diffusion in adsorbent, to increase graft type chitosan magnetic micro-sphere to Th4 +Adsorption capacity and adsorption rate.
Two, absorption test
Prepare the Th that 18 parts of 50ml initial concentrations are 3.0mmol/L4+Buffer is divided into two groups, and every group is used 1mol/L respectively
Hydrochloric acid or sodium hydroxide adjust pH be respectively 1,1.5,2,2.5,3,3.5,4,4.5,5.Take wherein one group of buffer add respectively
Enter graft type chitosan magnetic micro-sphere composite material made from 0.05g, it is poly- that 0.05g magnetic crust is separately added into another group of buffer
Sugared microballoon.It is respectively placed in water-bath constant temperature oscillator, keeping temperature is 25 DEG C, revolving speed 150r/min, after oscillation for 24 hours, uses magnetic
Iron separates graft type chitosan magnetic micro-sphere or chitosan magnetic micro-sphere from waste water, completes to Th4+Processing.With inductance coupling
Close Th unadsorbed in plasma spectrometer measurement waste water4+The adsorbance of content, calculating the results are shown in Table 1.
Table 1: different pH value are to Th in graft type chitosan magnetic micro-sphere removal waste water4+Influence
As shown in Table 1, pH value adsorbs Th to graft type chitosan magnetic micro-sphere4+Be affected, specific manifestation are as follows: in pH
When less than 2, chitosan magnetic micro-sphere and graft type chitosan magnetic micro-sphere are to Th4+Adsorption effect it is suitable；When pH is 2~3, branch
Type chitosan magnetic micro-sphere adsorption capacity increases sharply；When pH is 3.5~4.5, adsorption capacity rate of rise slows down, when pH is greater than
When 5, it will form precipitate metal hydroxides, therefore do not test.Chitosan magnetic micro-sphere is to Th4+Adsorption capacity pH be 1
When~2, Th is adsorbed with graft type chitosan magnetic micro-sphere4+Adsorbance it is close.But when pH is 2~5, chitosan magnetic micro-sphere
Adsorbance almost without growth, the adsorbance of graft type chitosan magnetic micro-sphere is apparently higher than chitosan magnetic micro-sphere.This is
Because of functional groups amino, carboxyl and carbon-carbon double bond on the polymer of graft type chitosan magnetic micro-sphere containing polycation, because
This absorption point is more, and the copolymerization of the itaconic acid containing a large amount of carboxyl functional groups and acrylic acid is introduced especially by graft copolymerization
Object can cooperate since the oxygen of carboxyl has non-bonding electrons with the unoccupied orbital of metal ion, form coordinate bond absorption, a Th4+From
It is sub to be coordinated with multiple electron carboxyl groups, form the chelate with cyclic structure.Additionally, due to Th4+With unreacted amine groups
Also it can be adsorbed by chelation.Therefore, graft type chitosan magnetic micro-sphere adsorption capacity is big, to the Th in waste water4+'s
Removal ability is preferable.
Three, Th is adsorbed4+Graft type chitosan magnetic micro-sphere parsing afterwards
Th will be adsorbed4+Graft type chitosan magnetic micro-sphere parsing afterwards, specific steps are as follows:
1) H of the EDTA and 0.1mol/L of 0.1mol/L are taken2SO4, acidity EDTA solution is prepared according to volume ratio 1:1；
2) absorption Th is taken4+Graft type chitosan magnetic micro-sphere 0.1g after saturation is mixed with 100mL acidity EDTA solution,
25 DEG C of oscillation 3h are extremely balanced.The adsorption capacity and desorption rate of graft type chitosan magnetic micro-sphere are as shown in table 2.The result shows that: it connects
Adsorption capacity of branch type chitosan magnetic micro-sphere is 2.525mmol/g, and adsorption capacity is after primary recycling
2.437mmol/g, regeneration rate are as follows: 96.5%；Adsorption capacity is 2.391mmol/g, regeneration rate are as follows: 94.7% after secondary recycling；
Adsorption capacity is 2.331mmol/g, regeneration rate are as follows: 92.3% after tertiary recycling.As it can be seen that graft type magnetic crust prepared by the present invention
Glycan microballoon has good regenerability, can be realized and is used repeatedly.
2 graft type chitosan magnetic micro-sphere of table is to Th4+Adsorption capacity and desorption rate
Graft type chitosan magnetic micro-sphere prepared by the present invention has good mechanical performance, can be used under acidic environment
Th4+Absorption, and adsorption capacity is big, to the Th in waste water4+Removal ability it is preferable.With EDTA fast desorption, Product recycling
Rate is high.It can be realized multiple utilization.It is recycled using the magnetic responsiveness of graft type chitosan magnetic micro-sphere, recycling is quick and returns
It receives at low cost, does not need special chemical industry equipment, it is easy to accomplish industrialized production.
Finally, it should be noted that technical side the above examples are only used to illustrate the technical scheme of the present invention and are not limiting
Case, those skilled in the art should understand that, modification or equivalent replacement of the technical solution of the present invention are made for those, and
The objective and range for not departing from the technical program, are intended to be within the scope of the claims of the invention.
Claims (8)
1. a kind of preparation method of graft type chitosan magnetic micro-sphere, which is characterized in that pass through Co deposited synthesis CoFe2O4It receives
Rice grain；Again by reversed emulsion polymerization, under the crosslinked action of glutaraldehyde, by chitosan and CoFe2O4Nano particle crosslinking
At chitosan magnetic micro-sphere, finally chitosan magnetic micro-sphere is grafted using itaconic acid and acrylic acid, obtains graft type magnetic
Property chitosan microball.
2. the preparation method of graft type chitosan magnetic micro-sphere according to claim 1, which is characterized in that specific steps
Are as follows:
(1) by FeCl3·6H2O and CoCl2·6H2O is dissolved in the ethylene glycol solution containing ammonium acetate, is stirred until being completely dissolved,
It is then transferred in reaction kettle, and reaction kettle is placed in 180 DEG C of baking oven, after heating reaction 20 ~ 24 hours, isolate precipitating
Object, after being washed with deionized water and dehydrated alcohol, frozen drying for 24 hours, obtains particle dispersion and uniform CoFe2O4Nanometer
Particle；
(2) chitosan is taken to be dissolved in the acetic acid solution that percentage by volume is 2%, it, will be in step (1) after stirring 6 ~ 12h
CoFe2O4Nano particle is added in above-mentioned solution, stirs 5 ~ 10h, obtains mixed solution；Hexamethylene and Span 80 are burnt in three necks
1 ~ 2h is stirred in bottle at 25 DEG C, the mixed solution is added, 3 ~ 6h is stirred, is warming up to 50 DEG C, adding mass fraction is 50%
Glutaraldehyde, stir 1h；Sediment is successively used ethyl alcohol, distillation water washing, 10 ~ 12h of frozen drying to get arrive magnetic crust
Glycan microballoon；
(3) it disperses the chitosan magnetic micro-sphere that step (2) obtain in the three-neck flask equipped with ultrapure water, leads to N2 30min is gone
Except oxygen in water, ammonium persulfate and sodium hydrogensulfite is added, in N2It is stirred 10 minutes under atmosphere, the clothing health of 0.1g/mL is added
Acid solution and acrylic acid, in 60 DEG C and N2After reacting 3 ~ 5h under atmosphere, sample is isolated with magnet, is repeatedly washed with ultrapure water,
And 10 ~ 12h of frozen drying to get arrive graft type chitosan magnetic micro-sphere.
3. the preparation method of graft type chitosan magnetic micro-sphere according to claim 1, which is characterized in that the step
(1) in, FeCl3·6H2O and CoCl2·6H2The molar ratio of O is 2 ~ 2.5:1, the quality of the ammonium acetate and ethylene glycol solution
Volume ratio is the mL of 1.16 ~ 2.32 g:25 ~ 50.
4. the preparation method of graft type chitosan magnetic micro-sphere according to claim 1, which is characterized in that the step
(1) in, reaction kettle is the stainless steel high-pressure hydrothermal reaction kettle of polytetrafluoroethyllining lining.
5. the preparation method of graft type chitosan magnetic micro-sphere according to claim 1, which is characterized in that the step
(2) in, the volume for the acetic acid solution that volume fraction is 2% and the mass ratio of chitosan are 40 ~ 50mL:1g；The CoFe2O4Nanometer
The mass ratio of particle and chitosan is 1:1.5 ~ 1.6；The volume ratio of hexamethylene and Span 80 is 100 ~ 200:0.7 ~ 1.3；Penta 2
The volume of aldehyde and 0.6 ~ 0.7ml:1g of mass ratio of chitosan.
6. the preparation method of graft type chitosan magnetic micro-sphere according to claim 1, which is characterized in that the step
(3) in, the ratio of chitosan magnetic micro-sphere and ultrapure water is 0.8 ~ 1.6g:75 ~ 150mL；Sodium hydrogensulfite and ammonium persulfate
The molar ratio of 0.7 ~ 0.75:1 of mass ratio, ammonium persulfate and chitosan is 0.5 ~ 0.6:1, chitosan, itaconic acid and acrylic acid
Mass ratio is 1:1.5 ~ 1.6:7 ~ 8.
7. a kind of be used to remove Th in waste water for graft type chitosan magnetic micro-sphere4+Application.
8. a kind of be used to remove Th in waste water for graft type chitosan magnetic micro-sphere4+Application, which is characterized in that the removal is
It is carried out under being 0 ~ 5.0 in pH value.
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