CN110090627A - A kind of calcium ion blotting chitosan adsorbent and the preparation method and application thereof - Google Patents
A kind of calcium ion blotting chitosan adsorbent and the preparation method and application thereof Download PDFInfo
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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Abstract
The invention discloses a kind of calcium ion blotting chitosan adsorbents and the preparation method and application thereof.Chitosan solution is uniformly mixed so as to obtain this method comprises: chitosan is added in acetum；Acrylic acid, template and initiator are added in chitosan solution, heating stirring under protective atmosphere obtains mixed liquor；Glutaraldehyde solution is added in mixed liquor, is mixed, heat treatment, centrifuging and taking precipitating is washed, dry；Precipitating is subjected to elution processing, obtains the calcium ion blotting chitosan adsorbent.This method is using calcium ion as template, glutaraldehyde as cross linker, and acrylic acid is that grafting agent has prepared the modification of chitosan nano adsorber that mechanical strength is strong, absorption property is good.Blotting chitosan adsorbent provided by the invention have many advantages, such as preparation is simple, adsorbent granule size uniformly, can with desorption and regeneration reuse, large specific surface area, adsorption effect it is good and selectively strong to object ion.The blotting chitosan adsorbent can have effectively achieved the removal of heavy metal ion.
Description
Technical field
The invention belongs to technical field of waste water processing, it is related to a kind of calcium ion template imprinting chitosan absorbent and its preparation
Method and application.
Background technique
With modern industrial or agricultural modernization, the development of urbanization, heavy metal pollution is very prominent.Currently, greatly
The technology of amount is applied to the removal of heavy metal ion in research water.Common processing method have chemical precipitation method, ion-exchange,
Electrochemical process and absorption method etc..In these techniques, due to absorption method have it is easy to operate, it is high-efficient, be easily recycled, it is renewable
The advantages that operating with no sludge has been considered as one of most common method.
Some researchers have attempted to develop the superperformance adsorbent for handling heavy metal ion.In these absorption
In agent, active carbon is considered as one of most effective removal of heavy metal ions adsorbent.Because of its specific surface area with higher
And adsorption capacity, but price is relatively expensive and is difficult to regenerate and easily cause secondary pollution, and which has limited its applications.
Shortcomings, FAQs have existing adsorbent in preparation and application process mostly: the absorption of sorbent material
Capacity is limited, not high to the adsorption capacity of heavy metal ion, rate of adsorption selectivity is not high, can not efficiently go out certain it is a kind of from
Son, functional graft be crosslinked more complicated, adsorbent stability it is not high and after being recycled absorption property reduce it is excessive etc..
Ideal removal of heavy metal ions adsorbent has characteristics that high surface area and high-adsorption-capacity, suitable hole
Diameter and volume, mechanical stability are easily obtained, and are easy to regenerate, and cost-effectiveness is environmental-friendly, simple process program and high selection
Property.Therefore, low-cost bio adsorbent especially chitosan (CS) attracts attention.But the machinery of chitosan is strong
Degree is not high, while in acid condition, the amino in molecule is easy to be protonated, so that chitosan be made to dissolve, causes chitosan
Loss.
Ionic imprinting technique is the branch of molecular imprinting technology, it, from for template, passes through electrostatic, coordination etc. with yin, yang
Action and function monomer interacts, and goes removing template empty with special groups arrangement, fixation from just obtaining after cross-linked polymeric
The rigid polymer of cave size and shape, the three-dimensional cavity of formation have specific selectivity to object ion, more and more by
Separation, enrichment aspect for metal ion.
Ionic imprinting technique, which is widely used in, prepares crosslink metallic complexing chitosan, has synthesized several metal shells
Chitosan material from aqueous solution to adsorb corresponding metal ion, such as Cu (II)-CS, Cd (II)-CS, Zn (II)-CS, Ag
(II)-CS, Ni (II)-CS and Pb (II)-CS.
The key point of crosslink metallic blotting chitosan is to enhance adsorption energy by the protection of the active site of metal complex
Power.Any metal ion that can form metal complex with chitosan can be used as theoretic template.But it is at present
Only, nearly all template ion delivered all is toxic heavy metal, and additional heavy metal consumption or discharge are inevitable.
Summary of the invention
In order to overcome the shortcomings of the prior art, the object of the present invention is to provide a kind of absorption of calcium ion blotting chitosan
Agent and preparation method thereof.
The disadvantages such as the present invention is complicated in order to solve existing chitosan absorbent preparation process, and selectivity is low, and mechanical strength is low,
The object of the present invention is to provide a kind of synthetic method is simple, selectivity is high, reusable modification of chitosan adsorbent.
The purpose of the present invention is realized at least through one of following technical solution.
A kind of preparation method of calcium ion blotting chitosan adsorbent provided by the invention, includes the following steps:
(1) chitosan is added in the container equipped with acetum, is placed on magnetic stirring apparatus and stirs evenly, makes chitosan
It is completely dissolved, obtains chitosan solution；
(2) acrylic acid, template and initiator are added in step (1) described chitosan solution, under protective atmosphere
Heating stirring processing, obtains mixed liquor；
(3) it in the step of glutaraldehyde solution being added (2) described mixed liquor, is uniformly mixed, heat treatment, after obtaining heating
Mixture；
(4) mixture after step (3) described heating is subjected to centrifugal treating, takes precipitating, washed, in a vacuum drying oven
It is dry；
(5) the calcium ion template adsorbent of step (4) after dry is immersed in hydrochloric acid solution, carries out elution processing, mistake
Leaching precipitating, washing are dried in a vacuum drying oven, obtain the calcium ion blotting chitosan adsorbent.
Further, the mass percent concentration of step (1) described acetum is 2%-4%；The chitosan is powder
Last shape, the deacetylating degree of chitosan are 85%-90%；The mass volume ratio of the chitosan and acetum is 1:70-
100g/mL。
Preferably, the time of step (1) described stirring is 20-30 minutes.
Further, the volume ratio of the acrylic acid and chitosan solution is 1:70-1:100.
Further, step (2) described template includes CALCIUM CHLORIDE DIHYDRATE (calcium ion template), the template
The mass volume ratio of quality and acrylic acid volume is 1:5-1:10g/mL.
Further, step (2) described initiator includes potassium peroxydisulfate and ammonium persulfate, it is preferable that initiator was selected
Potassium sulfate；The mass ratio of the initiator and template is 1:1-1:1.25；Step (2) described protective atmosphere includes nitrogen gas
Atmosphere；The stirring rate of the heating stirring processing is 600-1300rpm, and the time of the heating stirring processing is 2-3 hours,
The temperature of the heating stirring processing is 40-60 degrees Celsius.
Further, the mass percent concentration of step (3) described glutaraldehyde solution is 25%；The glutaraldehyde solution with
The volume ratio of mixed liquor is 1:70-2:70.
Further, it is 4-6 small that the temperature of step (3) described heat treatment, which is the time of 40-50 degrees Centigrade processing,
When.
Preferably, step (3) washing is to be washed with distilled water and dehydrated alcohol.
Further, the rate of step (4) described centrifugal treating is 8000-10000rmp；The time of centrifugal treating is 15-
35 minutes.
Preferably, the temperature of step (4) described drying is 60 degrees Celsius, and drying time is 4 hours.
Further, the concentration of step (5) described hydrochloric acid solution is 1-2mol/L；The time of the elution processing is 12-
24 hours.
Preferably, step (5) washing is precipitated to neutrality to be washed with distilled water.
Preferably, the temperature of step (5) described drying is 60 degrees Celsius, and drying time is 4 hours.
The present invention provides a kind of calcium ion blotting chitosan adsorbent as made from above-mentioned preparation method.
Calcium ion blotting chitosan adsorbent provided by the invention can be using in the treatment of waste water.
Raw materials of chitosan used in the present invention has the advantage that first, chitosan is by the de- of chitin
Acetylation production, chitin is most common biopolymer after cellulose；The second, since chitosan originates from life system
System external protective structures, therefore there is good biological degradability, biocompatibility and bioactivity；Third, because of chitosan
Amido and hydroxyl on chain can be used as the chelating site of metal ion, and chitosan can be used for collecting the suitable of metal ion
Polymer.
Preparation method provided by the invention improves chitosan bad mechanical strength and right using the method for physics and chemical modification
The disadvantages of pH variation is sensitive, is made a kind of calcium ion blotting chitosan adsorbent, with good adsorption effect and well
Mechanical strength.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) preparation method provided by the invention selects calcium ion for template, reduces the suction using heavy metal ion as template
Attached dose of preparation process pollutes environment bring；Using glutaraldehyde as cross linker, the mechanical strength of chitosan is increased, is improved
The diffluent problem of chitosan in acid condition；It uses acrylic acid for grafting material, increases the suction on modification of chitosan
Attached site enhances the adsorption capacity of modification of chitosan.
(2) calcium ion blotting chitosan adsorbent provided by the invention is to Hg2+With apparent selectivity, and adsorption capacity
It is apparently higher than natural chitosan；Under the conditions of 298K, to Hg2+Absorption reach as high as 555.56mg/g.
(3) calcium ion blotting chitosan adsorbent provided by the invention, is made of little particle of uniform size, and diameter is about
1um；Calcium ion blotting chitosan adsorbent (modification of chitosan adsorbent) surface area obviously increases, and is conducive to heavy metal
The absorption of ion；Adsorb Hg2+It is desorbed afterwards using EDTA, then adsorbs Hg again2+；Carry out new adsorption-desorption cycle 5
Secondary, adsorption capacity still keeps 80% or more, shows that the adsorbent has good reproducibility.
Specific embodiment
Specific implementation of the invention is described further below in conjunction with example, but implementation and protection of the invention is not limited to
This.If being that those skilled in the art can refer to prior art reality it is noted that there is the process of not special detailed description below
It is existing or understanding.Reagents or instruments used without specified manufacturer, being considered as can be by the commercially available conventional products being commercially available.
Embodiment 1
The calcium ion blotting chitosan adsorbent that embodiment 1 provides, preparation method include the following steps:
It (1) is 2% acetic acid by 1g chitosan (deacetylation of chitosan is 85%) addition 70mL mass percent concentration
In solution, stirring 30min is completely dissolved chitosan, stirs evenly, obtains chitosan solution；
(2) 1.0mL acrylic acid, 0.2g CALCIUM CHLORIDE DIHYDRATE and 0.2g initiator (potassium peroxydisulfate) are added to step (1)
In the chitosan solution, heating stirring is handled in a nitrogen atmosphere, and the temperature of heating stirring processing is 60 degrees Celsius, and heating is stirred
The stirring rate for mixing processing is 600rpm, and the time of heating stirring processing is 3 hours, obtains mixed liquor；
(3) the step of glutaraldehyde solution that 1.0mL mass percent concentration is 25% being added (2) described mixed liquor is (mixed
Liquid is closed through measuring, volume herein is 70mL) in, it is uniformly mixed, heat treatment, the temperature of heat treatment is 40 degrees Celsius, is added
The time of heat treatment is 6 hours, the mixture after being heated；
(4) mixture after step (3) described heating being subjected to centrifugal treating, the rate of centrifugal treating is 10000rpm,
The time of centrifugal treating is 15 minutes, takes precipitating, is washed with distilled water and dehydrated alcohol, is dried in a vacuum drying oven, dry
Temperature is 60 degrees Celsius, and drying time is 4 hours；
(5) precipitating of step (4) after dry is immersed in concentration is to carry out elution processing in 1mol/L hydrochloric acid solution, wash
The time of de- processing is 24 hours, filters to take precipitating, is washed with distilled water to neutrality, dries in a vacuum drying oven, dry temperature
Degree is 60 degrees Celsius, and drying time is 4 hours, obtains calcium ion blotting chitosan adsorbent (the novel agents of calcium ion trace shell
Glycan adsorbent).
Compliance test result: more parts above-mentioned of calcium ion blotting chitosan adsorbent of 0.02g is weighed respectively, is then respectively adding
50mL Pb containing 0.01mol/L2+Solution, 50mL contain 0.01mol/LHg2+Solution, 50mL contain 0.01mol/LCu2+It is molten
Liquid, 50mL contain 0.01mol/LCd2+Solution, 50mL contain 0.01mol/LNi2+Solution and 50mL contain 0.01mol/LCr2+'s
(anion of these solution is Cl in solution-).Then adsorption experiment (Staticadsorption experiment) is carried out under the conditions of 298K.With
EDTA titration tests adsorption effect, and absorption result is shown, the calcium ion blotting chitosan adsorbent that embodiment 1 provides is to Hg2+
Adsorption effect is best, Hg2+Adsorption capacity reach 421.3mg/g；The adsorption effect of remaining metal ion is good, wherein Pb2+'s
Adsorption capacity is 230mg/g, Cu2+Adsorption capacity be 47.8mg/g, Cd2+Adsorption capacity be 28.5mg/g, Ni2+Suction
Attached capacity 56.8mg/g is and Cr2+Adsorption capacity be 40.6mg/g.
The calcium ion blotting chitosan adsorbent is desorbed using EDTA, then with the calcium ion trace after desorption
Chitosan absorbent is to Hg2+Carry out adsorption experiment again (Staticadsorption experiment, experiment parameter are same as described above)；It repeats to inhale
After attached-de-adsorption cycle process 5 times, calcium ion blotting chitosan adsorbent is to Hg2+Adsorption capacity be 341.3mg/g；Still keep
80% or more, show that the adsorbent has good reproducibility, calcium ion blotting chitosan adsorbent is to it made from embodiment 1
He also has similar adsorption effect at heavy metal ion, can refer to Hg2+Absorption result.
Embodiment 2
The calcium ion blotting chitosan adsorbent that embodiment 2 provides, preparation method include the following steps:
It (1) is 3% acetic acid by 1g chitosan (deacetylation of chitosan is 87%) addition 80mL mass percent concentration
In solution, stirring 30min is completely dissolved chitosan, stirs evenly, obtains chitosan solution；
(2) 1.5mL acrylic acid, 0.215g CALCIUM CHLORIDE DIHYDRATE and 0.2g initiator (potassium peroxydisulfate) are added to step
(1) in the chitosan solution, heating stirring is handled in a nitrogen atmosphere, and the temperature of heating stirring processing is 50 degrees Celsius, is added
The stirring rate of thermal agitation processing is 800rpm, and the time of heating stirring processing is 2.5 hours, obtains mixed liquor；
It (3) is the step of 25% glutaraldehyde solution is added (2) described mixed liquor (mixing by 1.5mL mass percent concentration
For liquid through measuring, volume herein is 70mL) in, it is uniformly mixed, heat treatment, the temperature of heat treatment is 45 degrees Celsius, heating
The time of processing is 5 hours, the mixture after being heated；
(4) mixture after step (3) described heating being subjected to centrifugal treating, the rate of centrifugal treating is 9000rpm, from
The time of heart processing is 20 minutes, takes precipitating, is washed with distilled water and dehydrated alcohol, is dried in a vacuum drying oven, dry temperature
Degree is 60 degrees Celsius, and drying time is 4 hours；
(5) precipitating of step (4) after dry is immersed in concentration is to carry out elution processing in 1.5mol/L hydrochloric acid solution,
The time of elution processing is 20 hours, filters to take precipitating, is washed with distilled water to neutrality, dries in a vacuum drying oven, dry
Temperature is 60 degrees Celsius, and drying time is 4 hours, obtains calcium ion blotting chitosan adsorbent (the novel agents of calcium ion trace
Chitosan absorbent).
Compliance test result: more parts above-mentioned of calcium ion blotting chitosan adsorbent of 0.02g is weighed respectively, is then respectively adding
50mL Pb containing 0.01mol/L2+Solution, 50mL contain 0.01mol/LHg2+Solution, 50mL contain 0.01mol/LCu2+It is molten
Liquid, 50mL contain 0.01mol/LCd2+Solution, 50mL contain 0.01mol/LNi2+Solution and 50mL contain 0.01mol/LCr2+'s
(anion of these solution is Cl in solution-).Then adsorption experiment (Staticadsorption experiment) is carried out under the conditions of 298K.With
EDTA titration tests adsorption effect, and absorption result is shown, the calcium ion blotting chitosan adsorbent that embodiment 1 provides is to Hg2+
Adsorption effect is best, Hg2+Adsorption capacity reach 553.3mg/g；The adsorption effect of remaining metal ion is good, wherein Pb2+'s
Adsorption capacity is 389.8mg/g, Cu2+Adsorption capacity be 52.8mg/g, Cd2+Adsorption capacity be 32.5mg/g, Ni2+Suction
Attached capacity is 55.75mg/g and Cr2+Adsorption capacity be 50.7mg/g.
The calcium ion blotting chitosan adsorbent is desorbed using EDTA, then with the calcium ion trace after desorption
Chitosan absorbent is to Hg2+Carry out adsorption experiment again (Staticadsorption experiment, experiment parameter are same as described above)；It repeats to inhale
After attached-de-adsorption cycle process 5 times, calcium ion blotting chitosan adsorbent is to Hg2+Adsorption capacity be 472.2mg/g；Still keep
80% or more, show that the adsorbent has good reproducibility, calcium ion blotting chitosan adsorbent is to it made from embodiment 2
He also has similar adsorption effect at heavy metal ion, can refer to Hg2+Absorption result.
Embodiment 3
The calcium ion blotting chitosan adsorbent that embodiment 3 provides, preparation method include the following steps:
(1) vinegar for being 4% by 1g chitosan (deacetylation of chitosan is 90%) addition 100mL mass percent concentration
In acid solution, stirring 30min is completely dissolved chitosan, stirs evenly, obtains chitosan solution；
(2) 1.5mL acrylic acid, 0.25g CALCIUM CHLORIDE DIHYDRATE and 0.2g initiator (potassium peroxydisulfate) are added to step
(1) in the chitosan solution, heating stirring is handled in a nitrogen atmosphere, and the temperature of heating stirring processing is 60 degrees Celsius, is added
The stirring rate of thermal agitation processing is 1300rpm, and the time of heating stirring processing is 2 hours, obtains mixed liquor；
(3) the step of glutaraldehyde solution that 2.0mL mass percent concentration is 25% being added (2) described mixed liquor is (mixed
Liquid is closed through measuring, volume herein is 70mL) in, it is uniformly mixed, heat treatment, the temperature of heat treatment is 40 degrees Celsius, is added
The time of heat treatment is 6 hours, the mixture after being heated；
(4) mixture after step (3) described heating being subjected to centrifugal treating, the rate of centrifugal treating is 10000rpm,
The time of centrifugal treating is 15 minutes, takes precipitating, is washed with distilled water and dehydrated alcohol, is dried in a vacuum drying oven, dry
Temperature is 60 degrees Celsius, and drying time is 4 hours；
(5) precipitating of step (4) after dry is immersed in concentration is to carry out elution processing in 2mol/L hydrochloric acid solution, wash
The time of de- processing is 12 hours, filters to take precipitating, is washed with distilled water to neutrality, dries in a vacuum drying oven, dry temperature
Degree is 60 degrees Celsius, and drying time is 4 hours, obtains calcium ion blotting chitosan adsorbent (the novel agents of calcium ion trace shell
Glycan adsorbent).
Compliance test result: more parts above-mentioned of calcium ion blotting chitosan adsorbent of 0.02g is weighed respectively, is then respectively adding
50mL Pb containing 0.01mol/L2+Solution, 50mL contain 0.01mol/LHg2+Solution, 50mL contain 0.01mol/LCu2+It is molten
Liquid, 50mL contain 0.01mol/LCd2+Solution, 50mL contain 0.01mol/LNi2+Solution and 50mL contain 0.01mol/LCr2+'s
(anion of these solution is Cl in solution-).Then adsorption experiment (Staticadsorption experiment) is carried out under the conditions of 298K.With
EDTA titration tests adsorption effect, and absorption result is shown, the calcium ion blotting chitosan adsorbent that embodiment 1 provides is to Hg2+
Adsorption effect is best, Hg2+Adsorption capacity reach 501.3mg/g；The adsorption effect of remaining metal ion is good, wherein Pb2+'s
Adsorption capacity is 359.8mg/g, Cu2+Adsorption capacity be 48.8mg/g, Cd2+Adsorption capacity be 27.6mg/g, Ni2+'s
Adsorption capacity is 55.75mg/g and Cr2+Adsorption capacity be 45.7mg/g.
The calcium ion blotting chitosan adsorbent is desorbed using EDTA, then with the calcium ion trace after desorption
Chitosan absorbent is to Hg2+Carry out adsorption experiment again (Staticadsorption experiment, experiment parameter are same as described above)；It repeats to inhale
After attached-de-adsorption cycle process 5 times, calcium ion blotting chitosan adsorbent is to Hg2+Adsorption capacity be 421.1mg/g；Still keep
80% or more, show that the adsorbent has good reproducibility, calcium ion blotting chitosan adsorbent is to it made from embodiment 3
He also has similar adsorption effect at heavy metal ion, can refer to Hg2+Absorption result.
Comparative example 1
More parts of the above-mentioned chitosan of 0.02g (deacetylating degree of chitosan 87%) is weighed respectively, is then respectively adding 50mL
Pb containing 0.01mol/L2+Solution, 50mL contain 0.01mol/LHg2+Solution, 50mL contain 0.01mol/LCu2+Solution,
50mL contains 0.01mol/LCd2+Solution, 50mL contain 0.01mol/LNi2+Solution and 50mL contain 0.01mol/LCr2+Solution
In (anion of these solution is Cl-).Then adsorption experiment is carried out under the conditions of 298K, and (Staticadsorption experiment tests item
Part is identical as embodiment).Adsorption effect is tested with EDTA titration, absorption result is shown, chitosan pair described in comparative example 1
Hg2+Adsorption capacity be only 75.2mg/g；In remaining metal ion, Pb2+Adsorption capacity be only 77.9mg/g, Cu2+Suction
Attached capacity is only 32.0mg/g, Cd2+Adsorption capacity be only 19.5mg/g, Ni2+Adsorption capacity be only 54.0mg/g and Cr2+
Adsorption capacity be only 13.3mg/g.
The present invention is compared by embodiment 1-3 with the adsorption effect of comparative example 1, find calcium processed by the invention from
Sub- marking chitosan significantly improves the absorption property of heavy metal ion compared with natural chitosan.Meanwhile calcium ion trace shell
Glycan is selectively relatively high to mercury ion, and adsorption capacity is bigger.Adsorbent preparation process is simple, and renewable is strong.Therefore,
Calcium ion template chitosan has certain application prospect in terms of effluent containing heavy metal ions processing.
Above embodiments are only preferrred embodiment of the present invention, for explaining only the invention, are not intended to limit the present invention, this
Field technical staff should belong to guarantor of the invention without departing from change made under spirit of the invention, replacement, modification etc.
Protect range.
Claims (10)
1. a kind of preparation method of calcium ion blotting chitosan adsorbent, which comprises the steps of:
(1) chitosan is added in acetum, stirs evenly, obtains chitosan solution；
(2) acrylic acid, template and initiator are added in step (1) described chitosan solution, are heated under protective atmosphere
Stir process obtains mixed liquor；
(3) it in the step of glutaraldehyde solution being added (2) described mixed liquor, is uniformly mixed, heat treatment, it is mixed after being heated
Close object；
(4) mixture after step (3) described heating is subjected to centrifugal treating, takes precipitating, washed, it is dry；
(5) precipitating of step (4) after dry is immersed in hydrochloric acid solution, carries out elution processing, filter to take precipitating, wash, does
It is dry, obtain the calcium ion blotting chitosan adsorbent.
2. preparation method according to claim 1, which is characterized in that the mass percent of step (1) described acetum
Concentration is 2- 4%；The deacetylation of the chitosan is 85%-90%；The mass volume ratio of the chitosan and acetum is
1:70-100g/mL.
3. preparation method according to claim 1, which is characterized in that step (2) acrylic acid and chitosan solution
Volume ratio is 1:70-1:100；Step (2) described template includes CALCIUM CHLORIDE DIHYDRATE, the quality and acrylic acid of the template
The mass volume ratio of volume is 1:5-1:10 g/mL.
4. preparation method according to claim 1, which is characterized in that step (2) described initiator include potassium peroxydisulfate and
Ammonium persulfate；The mass ratio of the initiator and template is 1:1-1:1.25；Step (2) described protective atmosphere includes nitrogen gas
Atmosphere；The stirring rate of the heating stirring processing is 600-1300rpm, and the time of the heating stirring processing is 2-3 hours, institute
The temperature for stating heating stirring processing is 40-60 degrees Celsius.
5. preparation method according to claim 1, which is characterized in that the quality percentage of step (3) described glutaraldehyde solution
Specific concentration is 25%；The volume ratio of the glutaraldehyde solution and mixed liquor is 1:70-2:70.
6. preparation method according to claim 1, which is characterized in that the temperature of step (3) described heat treatment is 40-50
Degree Celsius；The time of heat treatment is 4-6 hours.
7. preparation method according to claim 1, which is characterized in that the rate of step (4) described centrifugal treating is 8000-
10000rmp；The time of centrifugal treating is time 15-35 minutes.
8. preparation method according to claim 1, which is characterized in that the concentration of step (5) described hydrochloric acid solution is 1-
2mol/L；The time of the elution processing is 12-24 hours.
9. a kind of calcium ion blotting chitosan adsorbent as made from claim 1-8 described in any item preparation methods.
10. the application of calcium ion blotting chitosan adsorbent as claimed in claim 9 in the treatment of waste water.
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