CN106944006A - A kind of preparation method and application of modified graphene oxide/Chitosan Composites - Google Patents
A kind of preparation method and application of modified graphene oxide/Chitosan Composites Download PDFInfo
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- CN106944006A CN106944006A CN201710202808.1A CN201710202808A CN106944006A CN 106944006 A CN106944006 A CN 106944006A CN 201710202808 A CN201710202808 A CN 201710202808A CN 106944006 A CN106944006 A CN 106944006A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of preparation method and application of modified graphene oxide/Chitosan Composites, comprise the following steps：EDTA modification, graphene oxide is modified, and modified graphene oxide is added into glacial acetic acid into ultrasound to uniform rear addition chitosan, scattered at a high speed, the shaping of modified graphene oxide/Chitosan Composites is carried out using high speed dispersor.The modified graphene oxide prepared using wet spinning technology/chitosan shaped composite material, a large amount of content functional groups are contained on surface to graphene oxide after modified, this functional group can not add the absorption property of composite under suboxides graphene content simultaneously and enhance the adhesion between graphene oxide and chitosan, increase substantially the mechanical strength of composite.The composite shows excellent adsorptive selectivity for heavy metal Hg, while being easy to the recycling of graphene oxide, solving graphene oxide is used for the problem that difficult recovery after water process causes secondary pollution.
Description
Technical field
The present invention relates to modified graphene oxide shaped composite material, and in particular to a kind of modified graphene oxide/shell gathers
The preparation method and application of sugared composite.
Background technology
Heavy metal pollution is worldwide economy and social concern, current processing method exist residual quantity it is high,
Heavy metal contaminants can not reclaim thoroughly, remain heavy metal causes secondary pollution problems to environment.Graphene oxide have than
Surface area is high, big to the heavy metal adsorption such as lead, cadmium, arsenic, mercury amount, the features such as remove thorough.For heavy metal processing, it is possible to resolve go
Except the key technology difficulty such as not thorough, realize that heavy metal contaminants 99% are reclaimed, heavy metal is thoroughly removed etc., major technique refers to
Mark obtains historic important breakthrough.But graphene oxide composite material sheet is unfavorable for sorbing material and heavy metal pollution as powder
The recovery of thing, forming processes need to be done to solve this problem to graphene oxide, but graphene oxide composite material is different from other carbon
Material is still without ripe forming technique.How to realize that graphene oxide can keep the excellent suction of heavy metal in water environment
Attached performance can recycle and not cause secondary pollution to environment again, become a great problem for being badly in need of solving instantly.
The content of the invention
In order to solve the deficiencies in the prior art, the invention provides a kind of modified graphite oxide adsorbed for heavy metal Hg
The preparation method of alkene/Chitosan Composites.
The technical solution adopted in the present invention is as follows：Step one：EDTA modification：By EDTA and silane coupler add to
In ethanol, stirred under uniform temperature, obtain mixed system A；Step 2：Graphene oxide is modified：A certain amount of graphene oxide is added
Enter into another ethanol ultrasound to being uniformly dispersed, obtain graphene oxide alcohol dispersion liquid B, A is mixed with B, uniform temperature is next time
Stream, suction filtration, products obtained therefrom is washed three times, and alcohol washes three times to obtain modified graphene oxide；Step 3：Modified graphene oxide is added
Enter into glacial acetic acid ultrasound to adding chitosan after uniform, using high speed dispersor carry out at a high speed it is scattered be sufficiently mixed it is former
Liquid C；Certain density alkaline solution is prepared for coagulating bath D；Step 4：Modified graphene oxide/Chitosan Composites into
Type：Stoste C is fitted into automatic injector and instilled stoste in coagulating bath D with certain fltting speed, is stood after completion of dropping,
It is washed with deionized after being taken out after stoste completely solidification to neutrality, low temperature drying can obtain ball-type modified graphene oxide/shell and gather
Sugared shaped composite material.
Preferably, the mass ratio of EDTA and silane coupler is 5 in the step one:1-1:5；In mixed system A
EDTA concentration is 10%-50%；2-24h is stirred at 20-80 DEG C.Wherein silane coupler be A-150, A-151, A-171,
A-1100, A-187, A-1891, A-189, A-1120, KH-550, KH-560, KH-590, KH-902, KH-903, in one kind
Or it is several.
Preferably, the concentration of graphene oxide alcohol dispersion liquid is 1%-10% in the step 2, ultrasonic time is
2-10h, EDTA in mass ratio when system A is mixed with system B:Graphene oxide=1:10-10:1, reflux temperature is after mixing
40-80 DEG C, return time is respectively to be washed three times with deionized water and ethanol after 4-24h, suction filtration.
Preferably, the concentration of glacial acetic acid is 10%-100% in the step 3；Modified graphene oxide glacial acetic acid point
The concentration of dispersion liquid is 1%-10%, and ultrasonic time is 2-10h；Quality compares chitosan：Modified graphene oxide=10:0.1-10:
3；The rotating speed of high-speed shearing machine turns for 200-2000, and shear time is 1-6h；Coagulating bath D is 5%-15% NaOH or KOH water
Solution.
Preferably, the fltting speed of syringe is 30-300 drops/min in the step 4；Shaping setting time is 10-
24h；The drying condition of the spherical composite of gained is the 30-50 DEG C of dry 2-10h in vacuum drying oven.
A kind of preparation method for the heavy metal Hg modified graphene oxide/Chitosan Composites adsorbed, including with
Lower step：
Step one：EDTA modification
It is 5 in mass ratio:1-1:5 weigh EDTA adds into ethanol in the lump with silane coupler；Wherein EDTA concentration
For 10%-50%；2-24h is stirred at 20-80 DEG C to be well mixed to obtain mixed system A both.
Step 2：The modification of graphene oxide
A certain amount of graphene oxide is weighed in another ethanol, the concentration of graphene oxide is 1%-10%, ultrasonic 2-
10h is uniformly dispersed to obtain graphene oxide alcohol dispersion liquid B, in mass ratio EDTA to graphene oxide:Graphene oxide=1:10-
10:1 mixes system A with system B, and mixing terminates rear suction filtration, products obtained therefrom after the 4-24h that flowed back in 40-80 DEG C of oil bath, backflow
Respectively washed with deionized water and ethanol three times it is standby.
Step 3：Spinning solution prepares
Weigh a certain amount of modified graphene oxide to be scattered in glacial acetic acid, the concentration of dispersion liquid is 1%-10%, ultrasound
2-10h is uniformly dispersed to modified graphene oxide；Chitosan in mass ratio：Modified graphene oxide=10:0.1-10:3 weigh
Chitosan is added into the glacial acetic acid dispersion liquid of modified graphene oxide；By high-speed shearing machine in the case where rotating speed turns for 200-2000
Shearing 1-6h obtains spinning solution C；NaOH the or KOH aqueous solution that compound concentration is 5%-15% is coagulating bath D.
Step 4：Forming processes
Spinning solution C in step 3 is fitted into automatic injector, the fltting speed of regulation automatic injector is 30-
300 drops/min；In the coagulating bath that spinning solution is added dropwise to NaOH the or KOH aqueous solution that concentration is 5%-15%, completion of dropping
10-24h is stood afterwards to filter after stoste drips off full solidification, is washed with deionized to neutrality, gained spheric granules is placed in very
30-50 DEG C of dry 2-10h in empty baking oven, obtains modified graphene oxide/chitosan shaped composite material.Above material is weighed
Metal adsorption experiment finds that its heavy metal mercury has excellent absorption property.
The beneficial effect that the technical scheme that the present invention is provided is brought is：Graphene oxide has larger specific surface area, compared with
Many functional group's heavy metals have an excellent absorption property, but itself are powder body material and are water-soluble, Adsorption of Heavy Metals
After be not easily recycled recycling cause secondary pollution increase processing cost.The present invention passes through silane coupler in surface of graphene oxide
Effect success grafting EDTA, roll up the oxygen-containing functional group on its surface, then mix with chitosan and pass through wet spinning means pair
Graphene oxide does forming processes.On the one hand the functionalization of graphene oxide adds absorption property the opposing party of graphene oxide
Face adds its hydrogen bond between chitosan so that this composite just shows excellent under graphene oxide very low content
Different absorption property.
Graphene oxide is carried out to facilitate the recycling after this material water process after forming processes, refuses secondary dirt
Dye；Adsorption capacity is stronger after graphene oxide grafting functional group, while also enhancing the hydrogen between graphene oxide and chitosan
Key is acted on, and strengthens composite material strength, and heavy metal Hg shows excellent adsorption effect.
The modified graphene oxide prepared using wet spinning technology/chitosan shaped composite material, graphene oxide warp
A large amount of content functional groups are contained on modified surface, and this functional group can not add the suction of composite under suboxides graphene content
Attached performance enhances the adhesion between graphene oxide and chitosan again simultaneously, and the machinery for increasing substantially composite is strong
Degree.The composite shows excellent adsorptive selectivity for heavy metal Hg, while being easy to the recovery of graphene oxide sharp again
With solving graphene oxide is used for the problem that difficult recovery after water process causes secondary pollution.
Brief description of the drawings
Fig. 1 is the structural representation of modified graphene oxide.
Fig. 2 is the structural representation of modified graphene oxide Adsorption of Heavy Metals.
Embodiment
Make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention is made further below
It is described in detail.
Embodiment 1：
A kind of preparation for the heavy metal Hg modified graphene oxide/Chitosan Composites adsorbed that the present invention is provided
Method, comprises the following steps：Step one：EDTA modification
It is 5 in mass ratio:1 weighs EDTA and KH-550 adds into ethanol in the lump；Wherein EDTA concentration is 20%；
12h is stirred at 80 DEG C to be well mixed to obtain mixed system A both.
Step 2：The modification of graphene oxide
A certain amount of graphene oxide is weighed in another ethanol, the concentration of graphene oxide is 10%, ultrasonic 10h to oxygen
Graphite alkene is uniformly dispersed to obtain graphene oxide alcohol dispersion liquid B, in mass ratio EDTA:Graphene oxide=1:10 by system A
Mixed with system B, mixing terminates rear suction filtration, products obtained therefrom deionized water and ethanol after the 4h that flowed back in 80 DEG C of oil baths, backflow
Respectively wash three times it is standby.
Step 3：Spinning solution prepares
Weigh a certain amount of modified graphene oxide to be scattered in glacial acetic acid, the concentration of dispersion liquid is 10%, and ultrasonic 10h is extremely
Modified graphene oxide is uniformly dispersed；Chitosan in mass ratio：Modified graphene oxide=10:3, which weigh chitosan, adds to changing
In the glacial acetic acid dispersion liquid of property graphene oxide；Spinning solution C is obtained for 2000 turns of down cuts 1 in rotating speed by high-speed shearing machine；
The NaOH aqueous solution that compound concentration is 5% is coagulating bath D.
Step 4：Forming processes
Spinning solution C in step 3 is fitted into automatic injector, regulation automatic injector fltting speed for 30 drop/
min；Spinning solution is added dropwise in the NaOH aqueous solution that concentration is 5%, 10h is stood after completion of dropping, treat that stoste is dripped off complete solidifying
Gu after filter, be washed with deionized to neutrality, gained spheric granules be placed in 30 DEG C of dry 10h in vacuum drying oven, modification is obtained
Graphene oxide/chitosan shaped composite material.Heavy metal adsorption experiment is carried out to above material.
Embodiment 2：
A kind of preparation for the heavy metal Hg modified graphene oxide/Chitosan Composites adsorbed that the present invention is provided
Method, comprises the following steps：Step one：EDTA modification
It is 1 in mass ratio:5 weigh EDTA and KH-560 adds into ethanol in the lump；Wherein EDTA concentration is 10%；
24h is stirred at 20 DEG C to be well mixed to obtain mixed system A both.
Step 2：The modification of graphene oxide
A certain amount of graphene oxide is weighed in another ethanol, the concentration of graphene oxide is 1%, ultrasonic 2h to oxidation
Graphene dispersion is uniform to obtain graphene oxide alcohol dispersion liquid B, in mass ratio EDTA:Graphene oxide=10:1 by system A with
System B is mixed, and mixing terminates rear suction filtration after the 24h that flowed back in 40 DEG C of oil baths, backflow, and products obtained therefrom deionized water and ethanol are each
Wash three times it is standby.
Step 3：Spinning solution prepares
Weigh a certain amount of modified graphene oxide to be scattered in glacial acetic acid, the concentration of dispersion liquid is 1%, ultrasonic 2h is to changing
Property graphene oxide is uniformly dispersed；Chitosan in mass ratio：Modified graphene oxide=10:0.1, which weighs chitosan, adds to changing
In the glacial acetic acid dispersion liquid of property graphene oxide；Spinning solution C is obtained for 200 turns of down cut 6h in rotating speed by high-speed shearing machine；
The KOH aqueous solution that compound concentration is 10% is coagulating bath D.
Step 4：Forming processes
Spinning solution C in step 3 is fitted into automatic injector, the fltting speed of regulation automatic injector is 300
Drop/min；Spinning solution is added dropwise in the KOH aqueous solution that concentration is 10%, 10h is stood after completion of dropping, treats that stoste is dripped off entirely
Filtered after solidification, be washed with deionized to neutrality, by gained spheric granules as 50 DEG C in vacuum drying oven dry 2h, obtain modification
Graphene oxide/chitosan shaped composite material.Heavy metal adsorption experiment is carried out to above material.
Embodiment 3：
A kind of preparation for the heavy metal Hg modified graphene oxide/Chitosan Composites adsorbed that the present invention is provided
Method, comprises the following steps：Step one：EDTA modification
It is 1 in mass ratio:1 weighs EDTA and A-150 adds into ethanol in the lump；Wherein EDTA concentration is 50%；
2h is stirred at 70 DEG C to be well mixed to obtain mixed system A both.
Step 2：The modification of graphene oxide
A certain amount of graphene oxide is weighed in another ethanol, the concentration of graphene oxide is 5%, ultrasonic 8h to oxidation
Graphene dispersion is uniform to obtain graphene oxide alcohol dispersion liquid B, in mass ratio EDTA:Graphene oxide=1:1 by system A and body
It is B mixing, mixing terminates rear suction filtration after the 14h that flowed back in 60 DEG C of oil baths, backflow, and products obtained therefrom is respectively washed with deionized water and ethanol
Three times standby.
Step 3：Spinning solution prepares
Weigh a certain amount of modified graphene oxide to be scattered in glacial acetic acid, the concentration of dispersion liquid is 6%, ultrasonic 6h is to changing
Property graphene oxide is uniformly dispersed；Chitosan in mass ratio：Modified graphene oxide=10:1, which weighs chitosan, adds to modification
In the glacial acetic acid dispersion liquid of graphene oxide；Spinning solution C is obtained for 1000 turns of down cut 3h in rotating speed by high-speed shearing machine；Match somebody with somebody
The NaOH aqueous solution that concentration processed is 15% is coagulating bath D.
Step 4：Forming processes
Spinning solution C in step 3 is fitted into automatic injector, the fltting speed of regulation automatic injector is 200
Drop/min；Spinning solution is added dropwise in the NaOH aqueous solution that concentration is 15%, 12h is stood after completion of dropping and treats that stoste is dripped off entirely
Filtered after solidification, be washed with deionized to neutrality, by gained spheric granules as 40 DEG C in vacuum drying oven dry 80h, must change
Property graphene oxide/chitosan shaped composite material.Heavy metal adsorption experiment is carried out to above material.
Embodiment 4：
A kind of preparation for the heavy metal Hg modified graphene oxide/Chitosan Composites adsorbed that the present invention is provided
Method, comprises the following steps：Step one：EDTA modification
It is 3 in mass ratio:2 weigh EDTA and KH-590 adds into ethanol in the lump；Wherein EDTA concentration is 40%；
11h is stirred at 50 DEG C to be well mixed to obtain mixed system A both.
Step 2：The modification of graphene oxide
A certain amount of graphene oxide is weighed in another ethanol, the concentration of graphene oxide is 7%, ultrasonic 4h to oxidation
Graphene dispersion is uniform to obtain graphene oxide alcohol dispersion liquid B, in mass ratio EDTA:Graphene oxide=5:1 by system A and body
It is B mixing, mixing terminates rear suction filtration after the 18h that flowed back in 50 DEG C of oil baths, backflow, and products obtained therefrom is respectively washed with deionized water and ethanol
Three times standby.
Step 3：Spinning solution prepares
Weigh a certain amount of modified graphene oxide to be scattered in glacial acetic acid, the concentration of dispersion liquid is 40%, and ultrasonic 7h is extremely
Modified graphene oxide is uniformly dispersed；Chitosan in mass ratio：Modified graphene oxide=5:1, which weighs chitosan, adds to modification
In the glacial acetic acid dispersion liquid of graphene oxide；Spinning solution C is obtained for 1500 turns of down cut 4h in rotating speed by high-speed shearing machine；Match somebody with somebody
The KOH aqueous solution that concentration processed is 8% is coagulating bath D.
Step 4：Forming processes
Spinning solution C in step 3 is fitted into automatic injector, the fltting speed of regulation automatic injector is 150
Drop/min；18h, which is stood, in the coagulating bath that spinning solution is added dropwise to the KOH aqueous solution that concentration is 8%, after completion of dropping treats stoste
Filter, be washed with deionized to neutrality after dripping off full solidification, by gained spheric granules as 45 DEG C in vacuum drying oven dry 7h,
Obtain modified graphene oxide/chitosan shaped composite material.Heavy metal adsorption experiment is carried out to above material.
Comparative example 1：
Step one：The preparation of EDTA solution
EDTA is weighed to add into ethanol；Wherein EDTA concentration is 10%；4h is stirred at 20 DEG C to being completely dissolved
System A.
Step 2：The modification of graphene oxide
A certain amount of graphene oxide is weighed in another ethanol, the concentration of graphene oxide is 1%, ultrasonic 2h to oxidation
Graphene dispersion is uniform to obtain graphene oxide alcohol dispersion liquid B, in mass ratio EDTA:Graphene oxide=10:1 by system A with
System B is mixed, and mixing terminates rear suction filtration after the 24h that flowed back in 40 DEG C of oil baths, backflow, and products obtained therefrom deionized water and ethanol are each
Wash three times it is standby.
Step 3：Spinning solution prepares
Weigh a certain amount of modified graphene oxide to be scattered in glacial acetic acid, the concentration of dispersion liquid is 1%, ultrasonic 2h is to changing
Property graphene oxide is uniformly dispersed；Chitosan in mass ratio：Modified graphene oxide=10:0.1, which weighs chitosan, adds to changing
In the glacial acetic acid dispersion liquid of property graphene oxide；Spinning solution C is obtained for 200 turns of down cut 6h in rotating speed by high-speed shearing machine；
The KOH aqueous solution that compound concentration is 10% is coagulating bath D.
Step 4：Forming processes
Spinning solution C in step 3 is fitted into automatic injector, the fltting speed of regulation automatic injector is 300
Drop/min；Spinning solution is added dropwise in the KOH aqueous solution that concentration is 10%, 10h is stood after completion of dropping, treats that stoste is dripped off entirely
Filtered after solidification, be washed with deionized to neutrality, by gained spheric granules as 50 DEG C in vacuum drying oven dry 2h, obtain modification
Graphene oxide/chitosan shaped composite material.Heavy metal adsorption experiment is carried out to above material.
Comparative example 2：
Step one：Spinning solution prepares
Weigh a certain amount of graphene oxide to be scattered in glacial acetic acid, the concentration of dispersion liquid is 6%, ultrasonic 6h is to aoxidizing stone
Black alkene is uniformly dispersed；Chitosan in mass ratio：Graphene oxide=10:1, which weighs chitosan, adds to modified graphene oxide
In glacial acetic acid dispersion liquid；Spinning solution C is obtained for 1000 turns of down cut 3h in rotating speed by high-speed shearing machine；Compound concentration is 15%
The NaOH aqueous solution be coagulating bath D.
Step 2：Forming processes
Spinning solution C in step 3 is fitted into automatic injector, the fltting speed of regulation automatic injector is 200
Drop/min；Spinning solution is added dropwise in the NaOH aqueous solution that concentration is 15%, 12h is stood after completion of dropping and treats that stoste is dripped off entirely
Filtered after solidification, be washed with deionized to neutrality, by gained spheric granules as 40 DEG C in vacuum drying oven dry 80h, must change
Property graphene oxide/chitosan shaped composite material.Heavy metal adsorption experiment is carried out to above material.
Carry out absorption property test to modified graphene oxide/chitosan shaped composite material, embodiment of the present invention 1-4 and
Technological parameter of comparative example and products thereof performance detection data comparing result is as shown in table 1.
Table 1：Embodiment and absorption property contrast
As can be seen from Table 1, the material prepared by embodiment is as many as 4 times of comparative example to Hg saturated extent of adsorption, this
It is primarily due to：1) directly graphene oxide is modified with EDTA in comparative example 1, is mainly EDTA carboxylic in modifying process
Esterification occurs for base and the hydroxyl of surface of graphene oxide, and is then first to add silane coupler to change EDTA in embodiment
Property, modified EDTA graftings to surface of graphene oxide mainly then be happens is that into silane coupler in this process again
Amino and surface of graphene oxide carboxyl occur amidation process, due to amino nucleophilicity be more than hydroxyl nucleophilicity,
The reaction in embodiment is caused to be more easy to progress, the functional group of surface of graphene oxide grafting is more than in comparative example, the absorption to Hg
Performance is stronger.2) graphene oxide does not pass through modification in comparative example 2, therefore its surface functional group after being combined with chitosan is more
Few, adhesion is also weaker, therefore absorption property is poor.
Claims (10)
1. a kind of preparation method of modified graphene oxide/Chitosan Composites, it is characterised in that：Comprise the following steps：
Step one：EDTA modification：EDTA and silane coupler are added into ethanol, is stirred under uniform temperature, obtains mixture
It is A；
Step 2：Graphene oxide is modified：A certain amount of graphene oxide is added into another ethanol ultrasound to being uniformly dispersed, obtained
Graphene oxide alcohol dispersion liquid B, A is mixed with B, is flowed back under uniform temperature, and suction filtration, products obtained therefrom is washed three times, and alcohol washes three
All over modified graphene oxide；
Step 3：Modified graphene oxide is added into glacial acetic acid ultrasound to uniform rear addition chitosan, high speed point is carried out
Dissipate be sufficiently mixed it stoste C；Certain density alkaline solution is prepared for coagulating bath D；
Step 4：The shaping of modified graphene oxide/Chitosan Composites：By stoste C with certain fltting speed by stoste
Instill in coagulating bath D, stood after completion of dropping, is washed with deionized after being taken out after stoste completely solidification to neutrality, low temperature dries
It is dry to obtain ball-type modified graphene oxide/chitosan shaped composite material.
2. a kind of preparation method of modified graphene oxide/Chitosan Composites according to claim 1, its feature exists
In：
In the step one, the mass ratio of EDTA and silane coupler is 5:1-1:5；EDTA concentration is in mixed system A
10%-50%；2-24h is stirred at 20-80 DEG C.
3. a kind of preparation method of modified graphene oxide/Chitosan Composites according to claim 1, its feature exists
In：In the step one, silane coupler is A-150, A-151, A-171, A-1100, A-187, A-1891, A-189, A-
One or more in 1120, KH-550, KH-560, KH-590, KH-902, KH-903.
4. a kind of preparation method of modified graphene oxide/Chitosan Composites according to claim 1, its feature exists
In：In the step 2, the concentration of graphene oxide alcohol dispersion liquid is 1%-10%, and ultrasonic time is 2-10h, system A with
EDTA in mass ratio when system B is mixed:Graphene oxide=1:10-10:1, reflux temperature is 40-80 DEG C after mixing, during backflow
Between be 4-24h.
5. a kind of preparation method of modified graphene oxide/Chitosan Composites according to claim 1, its feature exists
In：In the step 3, the concentration of glacial acetic acid is 10%-100%；The concentration of modified graphene oxide glacial acetic acid dispersion liquid is
1%-10%, ultrasonic time is 2-10h；Chitosan：Modified graphene oxide mass ratio=10:0.1-10:3.
6. a kind of preparation method of modified graphene oxide/Chitosan Composites according to claim 1, its feature exists
In：In the step 3, scattered at a high speed to use high-speed shearing machine, the rotating speed of high-speed shearing machine turns for 200-2000, shear time
For 1-6h；Coagulating bath D is the 5%-15% NaOH or KOH aqueous solution.
7. a kind of preparation method of modified graphene oxide/Chitosan Composites according to claim 1, its feature exists
In：In the step 4, syringe is used to instill stoste in coagulating bath D with certain fltting speed, fltting speed is 30-
300 drops/min.
8. a kind of preparation method of modified graphene oxide/Chitosan Composites according to claim 1, its feature exists
In：In the step 4, shaping setting time is 10-24h；The drying condition of the spherical composite of gained is in vacuum drying oven
30-50 DEG C of dry 2-10h.
9. modified graphene oxide/the Chitosan Composites prepared using such as any methods describeds of claim 1-8.
10. it is used for answering for heavy metal Hg absorption using modified graphene oxide/Chitosan Composites as claimed in claim 9
With.
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| CN107497404A (en) * | 2017-10-18 | 2017-12-22 | 中南林业科技大学 | A kind of preparation method of modified graphene oxide sorbing material |
| CN108905981A (en) * | 2018-07-12 | 2018-11-30 | 山东联星能源集团有限公司 | A kind of graphene/CNTs aeroge preparation method of low cost absorption heavy metal ion |
| CN112125586A (en) * | 2020-09-23 | 2020-12-25 | 常熟理工学院 | Preparation method and application of sulfhydryl modified graphene oxide nanosheet/geopolymer composite material |
| CN112226848A (en) * | 2020-09-03 | 2021-01-15 | 方大炭素新材料科技股份有限公司 | Chitosan-graphene oxide composite fiber and preparation method and application thereof |
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| CN113083238A (en) * | 2021-03-12 | 2021-07-09 | 华南理工大学 | Thiosemicarbazide functionalized graphene oxide/chitosan composite adsorbent and preparation method and application thereof |
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| CN107497404A (en) * | 2017-10-18 | 2017-12-22 | 中南林业科技大学 | A kind of preparation method of modified graphene oxide sorbing material |
| CN107497404B (en) * | 2017-10-18 | 2020-12-18 | 中南林业科技大学 | Preparation method of modified graphene oxide adsorption material |
| CN108905981A (en) * | 2018-07-12 | 2018-11-30 | 山东联星能源集团有限公司 | A kind of graphene/CNTs aeroge preparation method of low cost absorption heavy metal ion |
| CN112226848A (en) * | 2020-09-03 | 2021-01-15 | 方大炭素新材料科技股份有限公司 | Chitosan-graphene oxide composite fiber and preparation method and application thereof |
| CN112226848B (en) * | 2020-09-03 | 2022-11-29 | 方大炭素新材料科技股份有限公司 | Chitosan-graphene oxide composite fiber and preparation method and application thereof |
| CN112125586A (en) * | 2020-09-23 | 2020-12-25 | 常熟理工学院 | Preparation method and application of sulfhydryl modified graphene oxide nanosheet/geopolymer composite material |
| CN112125586B (en) * | 2020-09-23 | 2022-07-29 | 常熟理工学院 | Preparation method and application of sulfydryl modified graphene oxide nanosheet/geopolymer composite material |
| CN113083238A (en) * | 2021-03-12 | 2021-07-09 | 华南理工大学 | Thiosemicarbazide functionalized graphene oxide/chitosan composite adsorbent and preparation method and application thereof |
| CN113083238B (en) * | 2021-03-12 | 2022-07-26 | 华南理工大学 | Thiosemicarbazide functionalized graphene oxide/chitosan composite adsorbent and preparation method and application thereof |
| CN113072763A (en) * | 2021-04-23 | 2021-07-06 | 江西恒东管业有限公司 | Spiral winding Krah pipe and preparation method thereof |
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