CN109516535A - Flocculant and preparation method thereof - Google Patents
Flocculant and preparation method thereof Download PDFInfo
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- CN109516535A CN109516535A CN201710846559.XA CN201710846559A CN109516535A CN 109516535 A CN109516535 A CN 109516535A CN 201710846559 A CN201710846559 A CN 201710846559A CN 109516535 A CN109516535 A CN 109516535A
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Abstract
The present invention provides a kind of flocculants, the flocculant includes graphene quantum dot and the polymer that connect with the graphene quantum dot, wherein, the graphene quantum dot is graphene oxide quantum dot, the graphene oxide quantum dot contains the first active function groups, the polymer contains the second active function groups, and the graphene quantum dot and the polymer pass through first active function groups and second active function groups condensation connection.
Description
Technical field
The invention belongs to water environment treatment fields more particularly to a kind of flocculant and preparation method thereof.
Background technique
In recent years, graphene quantum dot material becomes more and more important in " quantum dot family " due to its excellent properties
A member.Graphene quantum dot material is mainly made of carbon, and carbon be to environment and human body " friendly element ", because
This, good environment and biological safety further promote the research promotion based on graphene quantum dot material.Especially work as
Graphene quantum spot size in 10nm or less, graphene quantum dot show big specific surface area, good mechanical plasticity,
Excellent thermo-chemical stability etc., these excellent properties make graphene mine quanta point material in environmental pollution improvement, photovoltaic, life
It is with a wide range of applications in the fields such as object imaging, sensor.
With the rapid development of industrial society, the living standard of the mankind has obtained considerable raising, but the following ring
Border pollution but becomes a urgent problem to be solved.In current environmental pollution, especially water pollution field, there is many dirts
Contaminate object and contaminating microorganisms, wherein most of contaminating microorganisms are by directlying adopt organic high molecular polymer as drug (wadding
Solidifying agent) it is administered.But using polymer as drug merely, that there are drug releases is fast, and release unevenly and does not have real-time positioning
The unfavorable results such as the features such as tracking causes contaminating microorganisms governance efficiency in water low, and cost increases.
Summary of the invention
The purpose of the present invention is to provide a kind of flocculants and preparation method thereof, it is intended to solve existing water pollution processing and use
Polymer directly as flocculant exist release is fast, release is uneven, cannot real-time location tracking, cause water pollution control to be imitated
The problem of rate is low, cost increases.
The invention is realized in this way one aspect of the present invention provides a kind of flocculant, the flocculant includes graphene
Quantum dot and the polymer being connect with the graphene quantum dot surface, wherein the graphene quantum dot is graphene oxide
The first active function groups are contained on quantum dot, the graphene oxide quantum dot surface, and the polymer contains the second active function
Group, the graphene quantum dot surface and the polymer pass through first active function groups and second active function groups
The group connection that condensation is formed.
Another aspect of the present invention provides a kind of preparation method of flocculant, comprising the following steps:
Graphene quantum dot is provided and polymer is mixed the graphene quantum dot and the mixed with polymers
Liquid, wherein the graphene quantum dot is graphene oxide quantum dot, and it is living that the graphene oxide quantum dot surface contains first
Property functional group, the polymer contain the second active function groups；
Make first active function groups and second active function groups that condensation reaction occur, makes the graphene quantum
Point is condensed the group to be formed with second active function groups by first active function groups with the polymer and connects, and makes
It is standby to obtain the flocculant.
Flocculant provided by the invention, has the advantage that
Graphene quantum dot (forms graphene oxide quantum dot) after being oxidized, itself is connected with the first active function groups
Pi bond is destroyed, and graphene quantum dot electron transport ability is caused to decline, and is affected the luminous intensity of graphene quantum dot and is shone
Efficiency, the graphene quantum dot and the polymer are contracted by first active function groups and second active function groups
Conjunction, which forms amide group, ester group, to form delocalized pi-bond with the pi bond of graphene quantum dot itself, and graphene amount can be improved by improving
The luminous efficiency and luminous intensity of son point；Further, after due to graphene quantum dot external connection polymer, graphite can be repaired
The defect of alkene quantum dot surface, luminous efficiency can be promoted further.Also, forming delocalized pi-bond may make flocculant of the invention
The flocculant, is distributed in sewage the effect that can play sustained release, and release by the intermolecular force enhancing between molecule
The rate put is also more evenly.Therefore, when the flocculant being used for water pollution control, tracking graphene quantum dot can be passed through
It shines to learn the graphene quantum dot real-time distribution of polymer connection, to realize the location tracking of flocculant.Of the invention
Flocculant is distributed in sewage, can achieve the purpose of medicament slow release and real-time location tracking, is effectively improved and is polluted micro- life in water
Object governance efficiency reduces treatment cost.
The preparation method of flocculant provided by the invention, easy to operate, favorable reproducibility.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The embodiment of the invention provides a kind of flocculant, the flocculant include graphene quantum dot and with the graphene
The polymer of quantum dot surface connection, wherein the graphene quantum dot is graphene oxide quantum dot, the graphene oxide
Quantum dot surface contains the first active function groups, and the polymer contains the second active function groups, the graphene quantum dot table
Face is condensed the group to be formed with second active function groups by first active function groups with the polymer and connects.
Flocculant provided in an embodiment of the present invention, has the advantage that
Graphene quantum dot (forms graphene oxide quantum dot) after being oxidized, itself is connected with the first active function groups
Pi bond is destroyed, and graphene quantum dot electron transport ability is caused to decline, and is affected the luminous intensity of graphene quantum dot and is shone
Efficiency, the graphene quantum dot and the polymer are contracted by first active function groups and second active function groups
Conjunction, which forms amide group, ester group, to form delocalized pi-bond with the pi bond of graphene quantum dot itself, and graphene amount can be improved by improving
The luminous efficiency and luminous intensity of son point；Further, after due to graphene quantum dot external connection polymer, graphite can be repaired
The defect of alkene quantum dot surface, luminous efficiency can be promoted further.Also, forming delocalized pi-bond may make flocculant of the invention
The flocculant, is distributed in sewage the effect that can play sustained release, and release by the intermolecular force enhancing between molecule
The rate put is also more evenly.Therefore, when the flocculant being used for water pollution control, tracking graphene quantum dot can be passed through
It shines to learn the graphene quantum dot real-time distribution of polymer connection, to realize the location tracking of flocculant.Of the invention
Flocculant is distributed in sewage, can achieve the purpose of medicament slow release and real-time location tracking, is effectively improved and is polluted micro- life in water
Object governance efficiency reduces treatment cost.
In the embodiment of the present invention, the selection of first active function groups and second active function groups, it is necessary to meet
Condensation reaction can occur between the two.Preferably, first active function groups are at least one in hydroxyl, carboxyl and aldehyde radical
Kind；Preferably, second active function groups are at least one in amide groups, imido grpup, amido, epoxy group, hydroxyl and ester group
Kind.Above-mentioned preferred first active function groups, the second active function groups have preferable reactivity, are conducive to pass through condensation reaction
The graphene quantum dot and the polymer are connected chemically.However, it is noteworthy that the described first active function
Group, second active function groups both need to first meet the premise that condensation reaction can occur, i.e., described first active function groups
At least one of condensation reaction can occur at least one of second active function groups.Such as first active function groups
When for carboxyl, second active function groups at least contain a kind of group that condensation reaction can occur with carboxyl, such as amide groups, Asia
Amido, amido, epoxy group, hydroxyl and ester group etc. on this basis, can also contain other groups certainly.
Specific preferred, the polymer is N- (3- dimethylamino-propyl) Methacrylamide, polyacrylamide, poly- two
Methylaminomethyl allylamine, polyethyleneimine, poly dimethyl aminopropyl methacrylamide, polypropylene oxide, poly- terephthaldehyde
At least one of sour glycol ester and polyethylene glycol.Preferred polymer, the regular oxidation base with graphene quantum dot surface
Group such as carboxyl, hydroxyl have preferable reactivity, are conducive to the progress of condensation reaction.When the polymeric oxidizer polyethyleneimine
It is solid under room temperature since the reactive group of L-PEI is secondary amine when amine, and contains in branch-like polyethyleneimine
There are primary amine, secondary amine and tertiary amine, is liquid under room temperature, it is therefore preferable that branch-like polyethyleneimine.
It is further preferred that the degree of polymerization of the polymer is 10~100, if the molecular weight of the polymer is too big, produce
Object is then excessively sticky, and polymer is not easy to react with quantum dot surface.In the preferred polymer of the embodiment of the present invention, branch
The shaped polyethylene imines degree of polymerization is 95, and polyethylene glycol polymeric degree is 75.
In the embodiment of the present invention, the mass ratio of the graphene quantum dot and the polymer is 1:1-1:50, it is preferred that
The mass ratio of the graphene quantum dot and the polymer is 1:1-1:30, so that it is suitable to obtain Connected degree, is had preferably point
The polymer for dissipating property connects graphene quantum dot.If the content of the polymer is too low, reaction not exclusively, makes as flocculant
Used time, both it had been unfavorable for the raising of flocculant sustained release performance, and had also been unfavorable for mentioning for graphene quantum dot luminous intensity and luminous efficiency
Height is unfavorable for the raising of real-time location tracking performance.If the too high levels of the polymer, the polymer of formation connects graphite
Alkene quantum dot dispersion performance is poor, is easy to happen coagulation, is unfavorable for in liquid-phase system.
Flocculant provided in an embodiment of the present invention can be prepared by following methods.
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of flocculant, comprising the following steps:
S01 provides graphene quantum dot and polymer is mixed the graphene quantum dot and the mixed with polymers
Close liquid, wherein the graphene quantum dot is graphene oxide quantum dot, and the graphene oxide quantum dot surface contains first
Active function groups, the polymer contain the second active function groups；
S02 makes first active function groups and second active function groups that condensation reaction occur, and makes the graphene
Quantum dot surface and the polymer are condensed the base to be formed by first active function groups and second active function groups
Group's connection, is prepared the flocculant.
The preparation method of flocculant provided in an embodiment of the present invention, easy to operate, favorable reproducibility, and prepared using this method
Flocculant out as flocculant in use, can achieve flocculant sustained release and real-time location tracking purpose, effectively improve water
Middle contaminating microorganisms governance efficiency reduces treatment cost.
Specifically, the graphene quantum dot is graphene oxide quantum dot, the graphite oxide in above-mentioned steps S01
Alkene quantum dot contains the first active function groups, and the polymer contains the second active function groups, first active function groups with
Condensation reaction can occur between second active function groups, i.e., at least one of described first active function groups can with it is described
Condensation reaction occurs for at least one of the second active function groups.When such as first active function groups are carboxyl, described second is living
Property functional group at least contain a kind of group that condensation reaction can occur with carboxyl, such as hydroxyl, amido.
Preferably, first active function groups are at least one of carboxyl and aldehyde radical；Preferably, second activity
Functional group is at least one of amide groups, imido grpup, amido, epoxy group, hydroxyl and ester group.
Specific preferred, the polymer is N- (3- dimethylamino-propyl) Methacrylamide, polyacrylamide, poly- two
Methylaminomethyl allylamine, polyethyleneimine, poly dimethyl aminopropyl methacrylamide, polypropylene oxide, poly- terephthaldehyde
At least one of sour glycol ester and polyethylene glycol.When the polymeric oxidizer polyethyleneimine, due to linear polyethylene
The reactive group of imines is secondary amine, is solid under room temperature, and contains primary amine, secondary amine and tertiary amine in branch-like polyethyleneimine,
It is liquid under room temperature, it is therefore preferable that branch-like polyethyleneimine.It is further preferred that the degree of polymerization of the polymer be 10~
100。
In the embodiment of the present invention, the graphene quantum dot is the graphene amount that marginal surface contains the first active function groups
Sub-, i.e., graphene passes through oxidation processes.
Preferably, the graphene oxide quantum dot the preparation method is as follows:
S011. graphene is placed in mixing concentrated acid and carries out oxidation processes, obtain graphene oxide；
S012. the graphene oxide is heated to 300-800 DEG C of progress calcination processing, prepares graphene oxide quantum
Point.
In above-mentioned steps S011, it is preferred that the mixing concentrated acid is concentrated nitric acid, dichromic acid, weight phosphoric acid, hydroiodic acid, Gao Meng
The mixed acid that at least one of acid, hydrobromic acid, perchloric acid, concentrated hydrochloric acid are formed with the concentrated sulfuric acid.Preferred mixing concentrated acid has very
Strong oxidisability can aoxidize to form the first active function groups on the surface of graphene, such as carboxyl, hydroxyl.It is further preferred that institute
It states in mixing concentrated acid, the volume ratio of the concentrated sulfuric acid and other acid is 1:1~1:100, more preferably 1:1~1:10, to assign
Give the mixing better reactivity of concentrated acid.Preferably, the concentration of the mixing concentrated acid is 6-8mol/L, to guarantee oxidation reaction
Go on smoothly.
In above-described embodiment, the graphene is 0.005-0.05g:1ml with the mass volume ratio for mixing concentrated acid, both
It can guarantee and oxidation reaction sufficiently occurs, nor it is excessively high to will cause acid concentration, remaining acid can influence production in following step
Moral character energy.
It is 1-24 hours, more preferably 5-12 hours by the time that graphene is placed in progress oxidation processes in mixing concentrated acid.
Oxidation reaction preferably using ultrasonic treatment, is conducive to graphene uniform, rapidly carries out surface oxidation.By oxidation processes, obtain
To the graphene for containing first active function groups.
In above-mentioned steps S012, by the graphene containing first active function groups be heated to 300-800 DEG C into
Row calcination processing, on the one hand, can remaining mixed acid in removal system by high-temperature heating；On the other hand, it is forged by high temperature
It burns, laminar structured graphene nanometer sheet occurs lamella dissociation, form graphene oxide under high temperature and organic solvent effect
Quantum dot.Also, in dissociation process, among quantum dot or edge can further generate some oxygen containing with organic solvent reaction
Graphene oxide quantum dot is prepared in active group.Preferably, the time of calcination processing is 10-60min.
It still more preferably, further include that the graphene quantum dot that will be obtained successively carried out after the calcination processing
Filter processing, dialysis treatment, wherein the filtration treatment realizes that the dialysis treatment is using retention using 0.2-50 μm of filter membrane
Molecular weight is that the bag filter of 1000-10000 dalton is realized.Wherein, using 0.2-50 μm of filter membrane by the bulky grain in system
Filtering removal, uses molecular cut off for the bag filter of 1000-10000 dalton, retains molecular weight ranges in 1000-10000
The graphene quantum dot of dalton screens out the too small or excessive graphene quantum dot of partial size, thus obtain particle diameter distribution uniformly,
And particle size range is in the graphene quantum dot of 10-30nm.Thus obtained graphene quantum dot, not only stability is good, and
And particle size range is suitable, reunites when can be connected chemically to avoid the too small graphene quantum dot of partial size, causes to connect
Chengwu is sticky, is unfavorable for the raising of its performance.
In the embodiment of the present invention, the mass ratio of the graphene quantum dot and the polymer is 1:1-1:50, preferably
1:1-1:30, to obtain, Connected degree is suitable, and there is the polymer of preferably dispersibility to connect graphene quantum dot.
By the graphene quantum dot and the mixed with polymers, following methods realization can be used: by the graphene amount
In deionized water, the polymer is added, until solution becomes clarification in the dispersion of son point under magnetic stirring；Or
In deionized water by graphene quantum dot dispersion, it is ultrasonically treated after the polymer is added, until solution
Become clarification.
Of course it is to be understood that the above-mentioned mixing processing mode enumerated, can only there is the mode for obtaining preferable mixed effect,
It is not used to limit all modes that the graphene quantum dot and the polymer are mixed to processing.
The mode that illumination or heating can be used makes first active function groups and second active function groups contract
Reaction is closed, the graphene quantum dot surface and the polymer is made to pass through first active function groups and second activity
Functional group is condensed the group to be formed connection.In a kind of specific embodiment, in above-mentioned steps S02, by the mixed liquor into
Row heating carries out condensation reaction, it is preferred that the temperature of the condensation reaction is 100-400 DEG C, reaction time 30-120min.
Reaction temperature of the embodiment of the present invention cannot be too high or too low, if reaction temperature is too low, is unfavorable for the progress of condensation reaction；If anti-
Answer temperature excessively high, then polymer is decomposed, and is readily incorporated other high temperature by-products.
It is further preferred that further including carrying out the pre-heat treatment, the pre-heat treatment to the mixed liquor before condensation reaction
Temperature be 40-100 DEG C, preheating time 10-60min.The embodiment of the present invention is first warming up to 40-100 DEG C of preheating 10-
60min can make graphene quantum dot to be reacted, polymer uniformly heat up before the reaction, prevent primary heating is too fast from leading
It causes reaction too fast, or even bumping occurs.Further, continue to heat up after reservation, the active official of the first of graphene quantum dot
It can roll into a ball and condensation reaction occurs under the conditions of 100-400 DEG C with the second active function groups of polymer, obtain polymer connection graphite
Alkene quantum dot.
Further, further include that the flocculant that will be prepared is further purified, reaction solution is such as subjected to column chromatography
Processing, the other impurities that removes extra polymer or may introduce collect product, dry.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of flocculant, comprising the following steps:
0.1g graphene nanometer sheet and 20ml mixing concentrated acid are added in beaker and carry out Oxidation at room temperature, wherein mixing concentrated acid
Combination is selected from the concentrated sulfuric acid and concentrated nitric acid, and graphene nanometer sheet is 0.005-0.05g/ml with the mass volume ratio for mixing concentrated acid；It is dense
Sulfuric acid and other sour mixed volume ratios are 1:4；Oxidization time is 10 hours.After ultrasonic treatment, it is put into equipped with waste gas recovering device
Muffle furnace in 400 DEG C calcine 20 minutes, obtain the graphene oxide quantum dot containing first active function groups such as carboxyl；
Graphene oxide is dispersed in distilled water, brown filtrate is obtained using 0.22 μm of filtering with microporous membrane, it will be brown
Color filtrate further uses the bag filter of 4000 dalton of molecular cut off to dialyse 5 hours, and uniform grading is obtained in bag filter
Purification of graphite oxide alkene quantum dot；
The purification of graphite oxide alkene quantum dot of 20mg uniform grading is dissolved in 20ml deionized water, in magnetic agitation state
Lower addition 0.15g polyethyleneimine, obtains mixed liquor, and graphene quantum dot and polyethyleneimine mass ratio are 1:13；
Liquid to be mixed is transferred in ptfe autoclave after mixing evenly, in Muffle furnace first with 80 DEG C under the conditions of protect
It holds 30 minutes, is then brought rapidly up to 230 DEG C and reacts 1 hour.The imido grpup of polyethyleneimine and the carboxyl of graphene quantum dot
Condensation reaction occurs；
After will be cooled to the reaction solution extra unreacted polyethyleneimine of column chromatographic column removing of room temperature, vacuum drying
Obtain the graphene quantum dot of polyethyleneimine connection.
Embodiment 2
A kind of preparation method of flocculant, comprising the following steps:
0.35g graphene nanometer sheet and 25ml mixing concentrated acid are added in beaker and carry out Oxidation at room temperature, wherein mixing concentrated acid
It combines and is selected from the concentrated sulfuric acid and concentrated hydrochloric acid, the mass volume ratio of graphene nanometer sheet and mixed acid is 0.005-0.05g/ml；Dense sulphur
Acid is 1:3 with other sour mixed volume ratios；Oxidization time is 8 hours.After ultrasonic treatment, it is put into the horse equipped with waste gas recovering device
Not 450 DEG C calcining 30 minutes in furnace, obtain the graphene oxide quantum dot containing first active function groups such as carboxyl；
Graphene oxide is dispersed in distilled water, brown filtrate is obtained using 0.22 μm of filtering with microporous membrane, it will be brown
Color filtrate further uses the bag filter of 5500 dalton of molecular cut off to dialyse 10 hours, and uniform grading is obtained in bag filter
Purification of graphite oxide alkene quantum dot；
The purification of graphite oxide alkene quantum dot of 20mg uniform grading is dissolved in 20ml deionized water, in magnetic agitation state
Lower addition 0.5g polyglycol solution, obtains mixed liquor, and the mass ratio of graphene quantum dot and polyethylene glycol is 1:25；
Liquid to be mixed is transferred in ptfe autoclave after mixing evenly, in Muffle furnace first with 80 DEG C under the conditions of protect
It holds 30 minutes, is then brought rapidly up to 350 DEG C and reacts 2.5 hours.The hydroxyl of polyethylene glycol and the carboxyl of graphene quantum dot are sent out
Raw condensation reaction；
After will be cooled to the reaction solution extra unreacted polyethylene glycol of column chromatographic column removing of room temperature, vacuum drying is
Obtain the graphene quantum dot of polyethylene glycol connection.
Embodiment 3
A kind of preparation method of flocculant, comprising the following steps:
0.25g graphene nanometer sheet and 20ml mixing concentrated acid are added in beaker and carry out Oxidation at room temperature, wherein mixing concentrated acid
Group is combined into the concentrated sulfuric acid and hydrobromic acid；The proportional region of graphene nanometer sheet and mixed acid is 0.005-0.05g/ml；The concentrated sulfuric acid with
Other sour mixed volume ratio 1:1~1:100, oxidization time 15 hours；
Mixed liquor is put into Ultrasound Instrument to be ultrasonically treated and is put into the Muffle furnace equipped with waste gas recovering device after a certain period of time
The regular hour is calcined to remove mixed acid, wherein muffle furnace is 400 DEG C；Calcination time is 50 minutes；It obtains containing carboxylic
The graphene oxide quantum dot of first active function groups such as base；
Resulting graphene oxide quantum dot is dispersed in distilled water again, obtains brown filter by filtering with microporous membrane
Liquid, for brown filtrate further with bag filter dialysis certain time, bag filter is interior to obtain graphene quantum dot.Miillpore filter diameter
It is 0.22 μm, dialysis bag retention molecular weight is 8000 dalton；Dialysis time is 30 hours；Obtain the purifying oxidation of uniform grading
Graphene quantum dot；
The purification of graphite oxide alkene quantum dot of 20mg uniform grading obtained above is dissolved in 20ml deionized water, in magnetic
0.35g polyacrylamide and 0.1g potassium hydroxide, graphene quantum dot and polyacrylamide matter are sequentially added under power stirring
Amount is than being 1:17.5；The mass ratio of graphene quantum dot and potassium hydroxide is 1:5；
Solution to step 4 is transferred in ptfe autoclave after mixing evenly, first with 90 DEG C of items in Muffle furnace
It is kept for 50 minutes under part, is then brought rapidly up to 350 DEG C and reacts 2.5 hours.The amide groups and graphene quantum of polyacrylamide
Condensation reaction occurs for the aldehyde radical of point；
The reaction solution that will be cooled to room temperature removes extra unreacted cationic polyacrylamide, vacuum with column chromatographic column
The graphene quantum dot of drying to obtain cationic polyacrylamide connection.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of flocculant, which is characterized in that the flocculant includes graphene quantum dot and connects with the graphene quantum dot
The polymer connect, wherein the graphene quantum dot is graphene oxide quantum dot, and the graphene oxide quantum dot surface contains
There are the first active function groups, the polymer contains the second active function groups, and the graphene quantum dot and the polymer are logical
It crosses first active function groups and is condensed the group to be formed with second active function groups and connect.
2. flocculant as described in claim 1, which is characterized in that first active function groups include in carboxyl and aldehyde radical
It is at least one；And/or
Second active function groups are at least one of amide groups, imido grpup, amido, epoxy group, hydroxyl and ester group.
3. flocculant as described in claim 1, which is characterized in that the polymer is N- (3- dimethylamino-propyl) methyl-prop
Acrylamide, polyacrylamide, poly dimethyl aminomethyl allylamine, polyethyleneimine, poly dimethyl aminopropyl methacrylamide,
At least one of polypropylene oxide, polyethylene terephthalate and polyethylene glycol.
4. flocculant as described in any one of claims 1-3, which is characterized in that the graphene oxide quantum dot and described poly-
The mass ratio for closing object is 1:1-1:30.
5. flocculant as described in any one of claims 1-3, which is characterized in that the degree of polymerization of the polymer is 10~100.
6. a kind of preparation method of the flocculant as described in claim 1-5 is any, which comprises the following steps:
Graphene quantum dot solution is provided and polymer is mixed the graphene quantum dot and the mixed with polymers
Liquid, wherein the graphene quantum dot is graphene oxide quantum dot, and it is living that the graphene oxide quantum dot surface contains first
Property functional group, the polymer contain the second active function groups；
Make first active function groups and second active function groups that condensation reaction occur, makes the graphene quantum dot table
Face is condensed the group to be formed with second active function groups by first active function groups with the polymer and connects, system
It is standby to obtain the flocculant.
7. the preparation method of flocculant as claimed in claim 6, which is characterized in that the temperature of the condensation reaction is 100-
400 DEG C, reaction time 30-120min.
8. the preparation method of flocculant as claimed in claim 7, which is characterized in that further include to described before condensation reaction
Mixed liquor carries out the pre-heat treatment, and the temperature of the pre-heat treatment is 40-100 DEG C, preheating time 10-60min.
9. such as the preparation method of the described in any item flocculants of claim 6-8, which is characterized in that the graphene oxide quantum
Point the preparation method is as follows:
Graphene is placed in mixing concentrated acid and carries out oxidation processes, obtains graphene oxide；
The graphene oxide is heated to 300-800 DEG C of progress calcination processing, graphene oxide quantum dot is prepared.
10. such as the preparation method of the described in any item flocculants of claim 6-8, which is characterized in that the mixing concentrated acid is dense
At least one of nitric acid, dichromic acid, weight phosphoric acid, hydroiodic acid, permanganic acid, hydrobromic acid, perchloric acid, concentrated hydrochloric acid are formed with the concentrated sulfuric acid
Mixed acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801286A (en) * | 2015-05-14 | 2015-07-29 | 安徽大学 | Graphene oxide hydroxy propyl cellulose composite hydrogel as well as preparing method and application thereof |
| CN105036269A (en) * | 2015-06-27 | 2015-11-11 | 李宏亮 | Multi-effect water treatment agent, preparation method thereof and water treatment method |
| CN105129901A (en) * | 2015-09-22 | 2015-12-09 | 陕西科技大学 | Grafted modified starch flocculating absorbent for tanning sewage and preparation method of flocculating absorbent |
| WO2016172755A1 (en) * | 2015-04-28 | 2016-11-03 | Monash University | Non-covalent magnetic graphene oxide composite material and method of production thereof |
| CN106536404A (en) * | 2014-05-26 | 2017-03-22 | 威廉马歇莱思大学 | Graphene quantum dot-polymer composites and methods of making the same |
-
2017
- 2017-09-19 CN CN201710846559.XA patent/CN109516535A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536404A (en) * | 2014-05-26 | 2017-03-22 | 威廉马歇莱思大学 | Graphene quantum dot-polymer composites and methods of making the same |
| WO2016172755A1 (en) * | 2015-04-28 | 2016-11-03 | Monash University | Non-covalent magnetic graphene oxide composite material and method of production thereof |
| CN104801286A (en) * | 2015-05-14 | 2015-07-29 | 安徽大学 | Graphene oxide hydroxy propyl cellulose composite hydrogel as well as preparing method and application thereof |
| CN105036269A (en) * | 2015-06-27 | 2015-11-11 | 李宏亮 | Multi-effect water treatment agent, preparation method thereof and water treatment method |
| CN105129901A (en) * | 2015-09-22 | 2015-12-09 | 陕西科技大学 | Grafted modified starch flocculating absorbent for tanning sewage and preparation method of flocculating absorbent |
Non-Patent Citations (1)
| Title |
|---|
| M.R. MANAFI ET AL.: "Synthesis of nanocomposites from polyacrylamide and graphene oxide:Application as flocculants for water purification", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
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