CN109261138A - It is a kind of for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon and preparation method thereof - Google Patents
It is a kind of for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon and preparation method thereof, and preparation method includes the following steps: (1) sodium alginate soln being added drop-wise to CaCl dropwise2It is stirring while adding in solution, carry out cross-linking reaction；It is filtered, washed after reaction, obtains sodium alginate micro ball；(2) sodium alginate micro ball is added in glutaraldehyde solution, adds hydrochloric acid, carry out aldehyde glycosylation reaction；It is filtered, washed, obtains the sodium alginate micro ball that aldehyde radical is contained on surface；(3) sodium alginate micro ball that aldehyde radical is contained on surface is put into ultrabranching polyamide solution, is filtered, washed, dries after reaction, obtain ultrabranching polyamide modified sodium alginate microballoon.Preparation method of the invention takes the balling-up of sodium alginate elder generation, and the strategy being grafted afterwards can make grafted moiety be fully exposed to microsphere surface, effectively increases the utilization rate of grafted moiety.
Description
Technical field
The present invention relates to the methods for preparing adsorbent for heavy metal more particularly to a kind of for heavy metal ion adsorbed
Ultrabranching polyamide modified sodium alginate microballoon and preparation method thereof.
Background technique
With the development of Chinese industrial, more and more heavy metals are discharged into environment, are caused serious heavy metal-polluted
Dye.Heavy metal ion has very high toxicity, it is difficult to biochemical degradation, can long-term existence in the natural environment, while food can be passed through
The constantly enrichment in vivo such as object chain, brings serious harm to natural environment and human health.Therefore, a huge sum of money how is reduced
Belong to ionic soil and effectively recycling heavy metal resources are the important topics that today's society faces.
Absorption method is widely adopted due to having many advantages, such as simple equipment, applied widely, high treating effect.Adsorbent is
Determine the key factor of high-effect adsorption treatment process.In conjunction with modern chemistry modification technology and Material cladding technology, develop it is inexpensive,
High-performance, reproducible environmentally friendly adsorbent are the key that heavy metal pollution control is ground with improvement and heavy metal adsorption
The developing direction studied carefully.
Natural biomass materials have many advantages, such as good biocompatibility, biodegradability, nontoxicity, thus by
Extensive concern.Biomass resource is used for the preparation of heavy metal ion adsorbing material, is on the one hand due to its molecular structure mesoporous
Porosity is higher, specific surface area is larger, physical absorption can occur with heavy metal ion；On the other hand, contain in biomass molecule structure
There is heavy metal ion adsorbed group abundant, such as-COOH ,-OH ,-NH2Deng can be inhaled by mode the effects of ion exchange, chelating
Attached heavy metal ion.
In numerous natural biomass materials, algae has the characteristic of good absorption soluble heavy metal, such as green alga
Good adsorption capacity is all showed to heavy metals such as arsenic, copper, lead, mercury, nickel.The alginic acid extracted from kelp or sargassum
Sodium, by the poly- beta-D-mannuronic acid of Isosorbide-5-Nitrae-(M unit) and α-L- guluronic acid (G unit) by Isosorbide-5-Nitrae-glucosides key connection, and
It is made of different GG, GM or MM segments with certain proportion.Containing a large amount of-OH ,-COO- isoreactivity functional groups in molecular structure, lead to
Forming salt can be reacted with heavy metal ion by crossing ion exchange or complexing, and can slough under certain conditions heavy metal from
Son regeneration.Sodium alginate itself have many advantages, such as good dissolubility, nontoxic, good biocompatibility, can natural degradation, therefore it is extensive
Research is used for heavy metal ion adsorbed field.
The sodium alginate of powder type is not easy to separate and recycle, therefore generally by the different crosslinking of sodium alginate
The absorption after perforated membrane, hydrogel or microballoon for heavy metal ion is made in agent.But the use of crosslinking agent can occupy sodium alginate
Functional group, influence its adsorption capacity to heavy metal.In order to overcome drawbacks described above, many researchs are concentrated on to sodium alginate
It is crosslinked again after carrying out functional group grafting, adds somewhat to the stability and absorption property of sodium alginate, but still
So there is certain deficiency: the functional group of grafting still some take part in crosslinking；Most of functional groups are embedded in
The inside of microballoon, only partial function group are exposed to play suction-operated in microsphere surface, and ideal adsorption effect is not achieved.
Therefore, it is one urgent that research and development, which have both the adsorbent for heavy metal of stability, low cost and high efficiency of additive capability,
Task.
Summary of the invention
The present invention provides a kind of for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon and its
Preparation method, the preparation method is simple and convenient, favorable reproducibility, the ultrabranching polyamide modified sodium alginate microballoon tool being prepared
There is efficient heavy ionic adsorption performance.
Specific technical solution is as follows:
A kind of preparation method for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon, including with
Lower step:
(1) sodium alginate soln is added drop-wise to CaCl dropwise2It is stirring while adding in solution, carry out cross-linking reaction；Reaction knot
It is filtered, washed after beam, obtains sodium alginate micro ball；
(2) sodium alginate micro ball is added in glutaraldehyde solution, adds hydrochloric acid, carry out aldehyde glycosylation reaction；It filters, wash
It washs, obtains the sodium alginate micro ball that aldehyde radical is contained on surface；
(3) sodium alginate micro ball that aldehyde radical is contained on surface is put into ultrabranching polyamide solution, after reaction mistake
Filter, washing, drying, obtain ultrabranching polyamide modified sodium alginate microballoon.
Primary raw material sodium alginate used in the present invention is the natural polysaccharide extracted from kelp or sargassum, source
Extensively, at the same have many advantages, such as good dissolubility, nontoxic, good biocompatibility, can natural degradation.Amide and amino-functional group can
Heavy metal ion is adsorbed by mode the effects of chelating, ion exchange, selects ultrabranching polyamide on sodium alginate micro ball surface
A large amount of amides and amino-functional group in grafting increase so that functional group is farthest exposed to sodium alginate micro ball surface
Strong adsorption effect of the microballoon to heavy metal ion.Preparation method of the invention is simple and convenient, favorable reproducibility, obtained hyperbranched
Polyamide modified sodium alginate micro ball has broad application prospects in effluent containing heavy metal ions process field.
In step (1), pass through CaCl2Sodium alginate is crosslinked, sodium alginate micro ball is formed, increases sodium alginate
Stability, while convenient for separation and being recycled after sodium alginate formation microballoon.
Preferably, in step (1), the concentration of sodium alginate soln is 1~5wt%, CaCl2The concentration of solution be 1~
10wt%；Sodium alginate soln and CaCl2The mass volume ratio of solution is 1: 1~5, unit g:mL；Further preferably, alginic acid
The concentration of sodium solution is 1~2wt%, CaCl2The concentration of solution is 1~5wt%；Sodium alginate soln and CaCl2The quality of solution
Volume ratio is 1: 1~1.5, unit g:mL.
Relative to sodium alginate concentration, if CaCl2Solution concentration is too low, then prepare it is micro-sphere crosslinked be not enough, cannot
Microballoon is formed well, and mechanical strength is also poor；If CaCl2Solution concentration is too high, will cause CaCl2Waste.
It is further preferred that the temperature of cross-linking reaction is room temperature in step (1), the time of cross-linking reaction is 5~7 hours.
Under the crosslinking condition, sodium alginate cross-linking is abundant, and stability is preferable.
In order to guarantee cross-linking effect, to CaCl2In solution be added dropwise sodium alginate soln when, mixing speed be 500~
1000rpm。
It is washed repeatedly after cross-linking reaction using deionized water, washes away extra CaCl2Solution.
In step (2), in sodium alginate micro ball surface grafting aldehyde radical, in order to further be grafted acyl on sodium alginate micro ball
Amine and amino-functional group provide basis.
Preferably, in step (2), in the glutaraldehyde solution, the concentration of glutaraldehyde is 0.1~1mol/L；Sodium alginate
Mass volume ratio with glutaraldehyde solution is 1: 25~50, unit g:mL；Further preferably, in the glutaraldehyde solution, penta 2
The concentration of aldehyde is 0.1~0.2mol/L；The mass volume ratio of sodium alginate and glutaraldehyde solution is 1: 25~50, unit g:
mL。
Here when the mass volume ratio of calculating sodium alginate and glutaraldehyde solution, the amount of sodium alginate is to prepare and add
The meter of used sodium alginate when sodium alginate micro ball.
Sodium alginate micro ball is further crosslinked using glutaraldehyde, on the one hand can be drawn on sodium alginate micro ball surface
Enter aldehyde functions, is conducive to ultrabranching polyamide and is grafted；On the other hand it can enhance sodium alginate micro ball to a certain extent
Mechanical strength.
It is further preferred that the concentration of hydrochloric acid is 1~1.2mol/L；The volume ratio of hydrochloric acid and glutaraldehyde solution be 1: 50~
100。
In aldol reaction, hydrochloric acid as catalyst, dosage within the above range when, can be only achieved preferable catalysis
Effect.
In step (2), the temperature of aldehyde glycosylation reaction is 55~65 DEG C, and the aldehyde radical reaction time is 5~7 hours.
In order to guarantee aldehyde radical effect, aldehyde glycosylation reaction is carried out under agitation, and mixing speed is 400~800rpm.
Aldehyde radicalization is washed with deionized water repeatedly after reaction, molten with the glutaraldehyde for removing sodium alginate micro ball surface
Liquid.
After sodium alginate micro ball aldehyde radical, then amide and amino-functional group are grafted on aldehyde radical.
Preferably, in step (3), the concentration of the ultrabranching polyamide solution is 2~40g/L；Sodium alginate and over-expense
The mass ratio for changing polyamide is 1: 0.1~2.
Here when the mass volume ratio of calculating sodium alginate and glutaraldehyde solution, the amount of sodium alginate is to prepare and add
The meter of used sodium alginate when sodium alginate micro ball.
The ultrabranching polyamide can be prepared by existing method, preferably be closed by diethylenetriamine and methyl acrylate
At.
Preferably, inherent viscosity of the ultrabranching polyamide at 30 DEG C is 0.0800~0.300dL/g.
When the viscosity of ultrabranching polyamide is larger, grafting amount is less, so that the sodium alginate micro ball counterweight finally obtained
The adsorption effect of metal ion is bad.
The experimental results showed that sodium alginate and ultrabranching polyamide mass ratio are too high or too low, what is be prepared is hyperbranched
Polyamide modified sodium alginate micro ball cannot all reach preferable heavy metal ion adsorbed effect.
In step (3), reaction temperature is 40~60 DEG C, and the reaction time is 1~2 hour.
In step (3), sodium alginate micro ball is dried using the method for freeze-drying, cryogenic temperature is -40~-20
℃；Cooling time is 12~24 hours.
In order to guarantee graft effect, graft reaction is carried out under agitation, and mixing speed is 200~400rpm.
After reaction, it is successively washed repeatedly with deionized water and ethyl alcohol, to remove the over-expense on sodium alginate micro ball surface
Change polyamide solution.
The invention also discloses the ultrabranching polyamide modified sodium alginate microballoons using preparation method preparation.This is super
Branched polyamide modified sodium alginate microballoon can be used for the heavy metal ion in adsorbed water body, the modified seaweed of the ultrabranching polyamide
Sour sodium micro-sphere structure is stablized, and adsorption effect is good.
Compared with prior art, the invention has the benefit that
(1) preparation method of the invention takes the balling-up of sodium alginate elder generation, and the strategy being grafted afterwards can make grafted moiety completely sudden and violent
It is exposed at microsphere surface, effectively increases the utilization rate of grafted moiety；After ultrabranching polyamide grafting, so that microsphere surface contains greatly
The amide and amino-functional group of amount effectively increase microballoon to the adsorption effect of heavy metal ion；With unmodified alginic acid
Sodium microballoon is compared, and the modified sodium alginate micro ball of ultrabranching polyamide improves 30~60% to the adsorbance of antimony ion, removal rate
Improve 30~60%；2~6 times are improved to the adsorbance of chromium ion, removal rate improves 2~6 times；
(2) preparation method of the invention is simple, and processing equipment requirement is low, reacts using water as medium, avoids expensive
And the use of harmful organic solvent, meet the requirement of Green Chemistry；
(3) it is the ultrabranching polyamide with efficient heavy ionic adsorption performance that preparation method of the invention, which is prepared,
Modified sodium alginate microballoon, it is cheap, it is convenient for industrialized production, use is safe, and storage and transportation is convenient, has good social benefit
And economic benefit.
Specific embodiment
Inherent viscosity of the ultrabranching polyamide used in following embodiment at 30 DEG C is 0.211dL/g.
Embodiment 1
(1) 2g sodium alginate powder is add to deionized water to the sodium alginate soln for being configured to 2wt%；Then dropwise
It is added to the CaCl of 5wt%2In solution, the mass volume ratio of the two is 1: 1.5, and stirring while adding, magnetic stirring speed is
800rpm, normal temperature crosslinked 7 hours, filtering, deionized water was washed repeatedly, obtained sodium alginate micro ball；
(2) sodium alginate micro ball is then put into 100mL concentration is that it is dense that 2mL is added in 0.2mol/L glutaraldehyde solution
Degree be 1mol/L hydrochloric acid, temperature keep 60 DEG C, magnetic agitation react 6 hours, magnetic stirring speed 600rpm, filtering, go from
Sub- water washing；Obtain the sodium alginate micro ball that aldehyde radical is contained on surface；
(3) sodium alginate micro ball that aldehyde radical is contained on surface is then put into the hyperbranched polyamides that 100mL concentration is 2g/L
In amine aqueous solution, temperature is kept for 60 DEG C, and magnetic agitation is reacted 2 hours, magnetic stirring speed 300rpm, through filtering, deionized water
It washs, ethanol washing, and is freeze-dried 12 hours in -40 DEG C repeatedly, obtain ultrabranching polyamide modified sodium alginate microballoon.
(4) by taking Sb (III) and Cr (VI) absorption as an example: taking sodium alginate micro ball and ultrabranching polyamide modified sodium alginate
Each 0.027g of microballoon, is put into 50mL vial, and Sb (III)/Cr (VI) solution that 10mL concentration is 200mg/L is added, adjusts
PH to 5.0/2.0, the oscillation absorption 26h at 30 DEG C.It is centrifuged, is filtered, by the Sb (III) in filtrate/Cr (VI) concentration dilution
To appropriate value.Using blank sample as reference, Sb (III) concentration is tested at 217.6nm with atomic spectrophotometer, 357.9
Cr (VI) concentration is tested at nm.
Under the above conditions, adsorbance (qe) and removal rate (R) are calculated, ultrabranching polyamide modified sodium alginate is compared
(HA@SA) microballoon and sodium alginate (SA) microballoon the results are shown in Table 1 to Sb (III), Cr (VI) adsorption effect.
Equilibrium adsorption capacity q is calculated as followseWith removal rate R:
Wherein, qeFor adsorbance, mg/g；R is removal rate, %；C0For the initial concentration for adsorbing preceding solution, mg/L；CeTo inhale
The equilibrium concentration of attached solution, mg/L；V is the volume of solution, L；M is the quality of adsorbent, g.
The adsorptivity of 1 sodium alginate micro ball of table and ultrabranching polyamide modified sodium alginate microballoon to Sb (III), Cr (VI)
Energy
As it can be seen from table 1 HA@SA microballoon is able to the absorption property of Sb (III), Cr (VI) compared with SA microballoon
It is promoted, wherein improving 35.34% to the adsorbance of Sb (III), removal rate improves 33.77%；The adsorbance of Cr (VI) is improved
2.06 times, removal rate improves 2.05 times.
Embodiment 2
(1) 2g sodium alginate powder is add to deionized water to the sodium alginate soln for being configured to 2wt%.Then dropwise
It is added to the CaCl of 1wt%2In solution, the mass volume ratio of the two is 1: 1, and stirring while adding, magnetic stirring speed is
800rpm, normal temperature crosslinked 6 hours, filtering, deionized water was washed repeatedly, obtained sodium alginate micro ball；
(2) sodium alginate micro ball is then put into 100mL concentration is that it is dense that 2mL is added in 0.19mol/L glutaraldehyde solution
Degree be 1mol/L hydrochloric acid, temperature keep 60 DEG C, magnetic agitation react 6 hours, magnetic stirring speed 600rpm, filtering, go from
Sub- water washs repeatedly, obtains the sodium alginate micro ball that aldehyde radical is contained on surface；
(3) sodium alginate micro ball that aldehyde radical is contained on surface is then put into the hyperbranched poly that 100mL concentration is 20 g/L
In amide solution, temperature is kept for 50 DEG C, and magnetic agitation is reacted 1 hour, magnetic stirring speed 300rpm, through filtering, deionization
Water washs repeatedly, ethanol washing, and is freeze-dried 24 hours in -40 DEG C, obtains ultrabranching polyamide modified sodium alginate microballoon.
(4) by taking Sb (III) and Cr (VI) absorption as an example: taking sodium alginate micro ball and ultrabranching polyamide modified sodium alginate
Each 0.027g of microballoon, is put into 50mL vial, and Sb (III)/Cr (VI) solution that 10mL concentration is 200mg/L is added, adjusts
PH 5.0/2.0, the oscillation absorption 26h at 30 DEG C.It is centrifuged, filters, the Sb (III) in filtrate/Cr (VI) concentration dilution is arrived
Appropriate value.Using blank sample as reference, Sb (III) concentration is tested at 217.6nm with atomic spectrophotometer, in 357.9nm
Place's test Cr (VI) concentration.
Under the above conditions, adsorbance (qe) and removal rate (R) are calculated, ultrabranching polyamide modified sodium alginate is compared
(HA@SA) microballoon and sodium alginate (SA) microballoon the results are shown in Table 2 to Sb (III), Cr (VI) adsorption effect.
The adsorptivity of 2 sodium alginate micro ball of table and ultrabranching polyamide modified sodium alginate microballoon to Sb (III), Cr (VI)
Energy
From table 2 it can be seen that HA@SA microballoon is able to the absorption property of Sb (III), Cr (VI) compared with SA microballoon
It is promoted, wherein improving 57.33% to the adsorbance of Sb (III), removal rate improves 55.50%；The adsorbance of Cr (VI) is improved
5.79 times, removal rate improves 5.79 times.
Embodiment 3
(1) 1g sodium alginate powder is add to deionized water to the sodium alginate soln for being configured to 1wt%.Then dropwise
It is added to the CaCl of 5wt%2In solution, the mass volume ratio of the two is 1: 1.2, and stirring while adding, magnetic stirring speed is
800rpm, normal temperature crosslinked 7 hours, filtering, deionized water was washed repeatedly, obtained sodium alginate micro ball；
(2) sodium alginate micro ball is then put into 100mL concentration is that it is dense that 2mL is added in 0.2mol/L glutaraldehyde solution
Degree be 1mol/L hydrochloric acid, temperature keep 60 DEG C, magnetic agitation react 6 hours, magnetic stirring speed 600rpm, filtering, go from
Sub- water washs repeatedly, obtains the sodium alginate micro ball that aldehyde radical is contained on surface；
(3) sodium alginate micro ball that aldehyde radical is contained on surface is then put into the hyperbranched poly that 100mL concentration is 30g/L
In amide solution, temperature is kept for 50 DEG C, and magnetic agitation is reacted 1 hour, magnetic stirring speed 300rpm, through filtering, deionization
Water washs repeatedly, ethanol washing, and is freeze-dried 24 hours in -20 DEG C, obtains ultrabranching polyamide modified sodium alginate microballoon.
(4) by taking Sb (III) and Cr (VI) absorption as an example: taking sodium alginate micro ball and ultrabranching polyamide modified sodium alginate
Each 0.027g of microballoon, is put into 50mL vial, and Sb (III)/Cr (VI) solution of 10mL 200mg/L is added, and adjusts pH
5.0/2.0, the oscillation absorption 26h at 30 DEG C.Be centrifuged, filter, by the Sb (III) in filtrate/Cr (VI) concentration dilution to fit
Work as value.Using blank sample as reference, Sb (III) concentration is tested at 217.6nm with atomic spectrophotometer, at 357.9nm
Test Cr (VI) concentration.
Under the above conditions, adsorbance (qe) and removal rate (R) are calculated, ultrabranching polyamide modified sodium alginate is compared
(HA@SA) microballoon and sodium alginate (SA) microballoon the results are shown in Table 3 to Sb (III), Cr (VI) adsorption effect.
The adsorptivity of 3 sodium alginate micro ball of table and ultrabranching polyamide modified sodium alginate microballoon to Sb (III), Cr (VI)
Energy
From table 3 it can be seen that HA@SA microballoon is able to the absorption property of Sb (III), Cr (VI) compared with SA microballoon
It is promoted, wherein improving 35.62% to Sb (III) adsorbance, removal rate improves 47.18%；The adsorbance of Cr (VI) is improved
5.10 times, removal rate improves 5.29 times.
Embodiment 4
(1) 1.5g sodium alginate powder is add to deionized water to the sodium alginate soln for being configured to 1.5wt%.Then
It is added dropwise to the CaCl of 2wt%2In solution, the mass volume ratio of the two is 1: 1.3, stirring while adding, magnetic stirring speed
For 800rpm, normal temperature crosslinked 6 hours, filtering, deionized water was washed repeatedly, obtained sodium alginate micro ball；
(2) sodium alginate micro ball is then put into 100mL concentration is that it is dense that 2mL is added in 0.15mol/L glutaraldehyde solution
Degree be 1mol/L hydrochloric acid, temperature keep 60 DEG C, magnetic agitation react 6 hours, magnetic stirring speed 600rpm, filtering, go from
Sub- water washs repeatedly, obtains the sodium alginate micro ball that aldehyde radical is contained on surface；
(3) the hyperbranched polyamides for being then 10g/L by the sodium alginate micro ball investment 100mL concentration that aldehyde radical is contained on surface
In amine aqueous solution, temperature is kept for 50 DEG C, and magnetic agitation is reacted 1 hour, magnetic stirring speed 300rpm, through filtering, deionized water
It washs, ethanol washing, and is freeze-dried 12 hours in -20 DEG C repeatedly, obtain ultrabranching polyamide modified sodium alginate microballoon.
(4) by taking Sb (III) and Cr (VI) absorption as an example: taking sodium alginate micro ball and ultrabranching polyamide modified sodium alginate
Each 0.027g of microballoon, is put into 50mL vial, and Sb (III)/Cr (VI) solution that 10mL concentration is 200mg/L is added, adjusts
PH 5.0/2.0, the oscillation absorption 26h at 30 DEG C.It is centrifuged, filters, the Sb (III) in filtrate/Cr (VI) concentration dilution is arrived
Appropriate value.Using blank sample as reference, Sb (III) concentration is tested at 217.6nm with atomic spectrophotometer, in 357.9nm
Place's test Cr (VI) concentration.
Under the above conditions, adsorbance (qe) and removal rate (R) are calculated, ultrabranching polyamide modified sodium alginate is compared
(HA@SA) microballoon and sodium alginate (SA) microballoon the results are shown in Table 4 to Sb (III), Cr (VI) adsorption effect.
The adsorptivity of 4 sodium alginate micro ball of table and ultrabranching polyamide modified sodium alginate microballoon to Sb (III), Cr (VI)
Energy
From table 4, it can be seen that HA@SA microballoon can be able to the adsorptivity of Sb (III), Cr (VI) compared with SA microballoon
It is promoted, wherein improving 30.27% to the adsorbance of Sb (III), removal rate improves 40.70%；The adsorbance of Cr (VI) is improved
3.22 times, removal rate improves 3.30 times.
Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that
Above is only a specific embodiment of the present invention, it is not intended to restrict the invention, it is all to be done in spirit of the invention
Any modification, supplementary, and equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon, feature exist
In, comprising the following steps:
(1) sodium alginate soln is added drop-wise to CaCl dropwise2It is stirring while adding in solution, carry out cross-linking reaction；After reaction
It is filtered, washed, obtains sodium alginate micro ball；
(2) sodium alginate micro ball is added in glutaraldehyde solution, adds hydrochloric acid, carry out aldehyde glycosylation reaction；It is filtered, washed,
Obtain the sodium alginate micro ball that aldehyde radical is contained on surface；
(3) sodium alginate micro ball that aldehyde radical is contained on surface is put into ultrabranching polyamide solution, filters, washes after reaction
It washs, dry, obtain ultrabranching polyamide modified sodium alginate microballoon.
2. the system according to claim 1 for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon
Preparation Method, which is characterized in that in step (1), the concentration of sodium alginate soln is 1~5wt%, CaCl2The concentration of solution be 1~
10wt%；Sodium alginate soln and CaCl2The mass volume ratio of solution is 1: 1~5, unit g: mL.
3. according to claim 1 or 2 be used for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon
Preparation method, which is characterized in that in step (1), the temperature of cross-linking reaction is room temperature, and the time of cross-linking reaction is 5~7 small
When.
4. the system according to claim 1 for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon
Preparation Method, which is characterized in that in step (2), in the glutaraldehyde solution, the concentration of glutaraldehyde is 0.1~1mol/L；Alginic acid
The mass volume ratio of sodium and glutaraldehyde solution is 1: 25~50, unit g: mL.
5. the system according to claim 4 for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon
Preparation Method, which is characterized in that in step (2), the concentration of hydrochloric acid is 1~1.2mol/L；The volume ratio of hydrochloric acid and glutaraldehyde solution
It is 1: 50~100.
6. according to claim 1, micro- for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate described in 4 or 5
The preparation method of ball, which is characterized in that in step (2), the temperature of aldehyde glycosylation reaction is 55~65 DEG C, and the aldehyde radical reaction time is
5~7 hours.
7. the system according to claim 1 for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon
Preparation Method, which is characterized in that in step (3), the concentration of the ultrabranching polyamide solution is 2~40g/L；Sodium alginate and super
The mass ratio of branched polyamide is 1: 0.1~2.
8. according to claim 1 or claim 7 be used for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon
Preparation method, which is characterized in that in step (3), reaction temperature be 40~60 DEG C, the reaction time be 1~2 hour.
9. according to claim 1 or claim 7 be used for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon
Preparation method, which is characterized in that in step (3), sodium alginate micro ball is dried using the method for freeze-drying, freeze
Temperature is -40~-20 DEG C；Cooling time is 12~24 hours.
10. a kind of for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon, which is characterized in that by right
It is required that 1~9 described in any item preparation methods are made.
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