CN106745463A - A kind of sewage water treatment method of utilization reducing agent in-situ reducing graphene oxide - Google Patents
A kind of sewage water treatment method of utilization reducing agent in-situ reducing graphene oxide Download PDFInfo
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- CN106745463A CN106745463A CN201710048173.4A CN201710048173A CN106745463A CN 106745463 A CN106745463 A CN 106745463A CN 201710048173 A CN201710048173 A CN 201710048173A CN 106745463 A CN106745463 A CN 106745463A
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- graphene oxide
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- reducing agent
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
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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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of high-efficiency sewage processing method of utilization metal simple-substance reducing agent in-situ reducing graphene oxide, its object is to by when graphene oxide processes sewage, add reducing agent and catalyst, in-situ reducing graphene oxide, greatly increases adsorption efficiency and adsorption capacity of the Graphene to dirty water pollutant.The method includes the pigment (dye of positive ion to multiple pollutant object：Methylene blue MB；Anionic dye：Congo red CR, lemon yellow LY) and heavy metal ion (Cd2+, Pb2+) pollutant adsorption efficiency close to 100%, adsorption capacity improves several times to hundred times than the grapheme material of prior art.The present invention is a kind of sewage disposal new method of environmental protection and economy, can be with green, the supper-fast, pigment efficiently removed in water body, heavy metal or other pollutants.
Description
Technical field
It is in situ using reducing agent more particularly, to one kind the invention belongs to water body purification and environmental protection technical field
The sewage water treatment method of redox graphene.
Background technology
With the development of human society industrial or agricultural, China is faced with the environmental problem that water pollution etc. is on the rise.Pigment
In often coexisting in water body environment with heavy metal, these environmental contaminants have a high toxicity, carcinogenicity, non-biodegradable and easily exist
The harm such as enrichment, huge harm is caused to health and environment in organism.In view of this harm seriousness and
Strict standard has been formulated in chronicity, green harmless treatment of the government to the waste water containing pigment and heavy metal, therefore in discharge
Be must go to before sewage except these pollutants.Purification pigment and heavy metal ion polluted-water have various methods, and for example chemistry is heavy
The methods such as shallow lake, UF membrane, filtering, ion exchange, electrodialysis and absorption slow down environmental pollution, and adsorbent is inhaled in these methods
Attached is a kind of efficient sewage water treatment method.The active charcoal of adsorbent main at present, metal oxide, functional silica gel and oxygen
Graphite alkene and graphene-based material etc., therefore adsorption treatment on sewage has the adsorbent of multiple types concurrently, it is efficiently, easily separated, it is easy to
The advantages of operation and relatively low cost.Graphene oxide and graphite alkenyl nanometer materials have special two-dimensional structure, various
The characteristic such as oxygen-containing functional group and great specific surface area, is optimal candidate material in adsorbent.But, existing Graphene material
The shortcomings of expecting that sewage treatment method is present costly, time-consuming, treatment pollutant object is single, and easily cause secondary pollution.
Therefore, how economic green, quickly and efficiently remove the focus that pigment and metal ion in sewage are still mankind's concern simultaneously
Problem.
Based on graphene oxide, pigment and heavy metal ion have preferable absorption property in sewage is processed, it has been found that
Can greatly increase adsorption efficiency and adsorption capacity using zinc powder in-situ reducing graphene oxide.This work disposal is more
Planting pollutant object includes the pigment (dye of positive ion：Methylene blue MB；Anionic dye：Congo red CR, lemon yellow LY) and weight
Metal ion (Cd2+,Pb2+), the method is to the adsorption efficiency of these pollutants close to 100%.We have developed a kind of environmental protection warp
The sewage disposal new method of Ji, can be supper-fast with green, efficiently removes pigment and heavy metal in water body.
The content of the invention
It is former using metal simple-substance reducing agent the invention provides one kind for the disadvantages described above or Improvement requirement of prior art
The high-efficiency sewage processing method of position redox graphene, its object is to by when graphene oxide processes sewage, adding
Reducing agent and catalyst, in-situ reducing graphene oxide, greatly increase Graphene to the adsorption efficiency of dirty water pollutant and
Adsorption capacity, thus solve prior art using grapheme material treatment sewage adsorption capacity it is low, adsorption efficiency is low, time-consuming
Technical problem.
To achieve the above object, according to one aspect of the present invention, there is provided one kind is using the oxidation of reducing agent in-situ reducing
The sewage water treatment method of Graphene, under agitation, to addition graphene oxide and reducing agent, separation of solid and liquid, institute in sewage
It is the sewage after treatment to obtain liquid phase；The reducing agent is used for in-situ reducing graphene oxide.
Preferably, the reducing agent is metal simple-substance that normal reduction potential is -2.5V~-0.4V.
Preferably, the reducing agent is at least one in magnesium powder, aluminium powder, zinc powder and iron powder.
Preferably, the reducing agent is zinc powder.
Preferably, catalyst has been additionally added in the sewage, the reduction that the catalyst is used to be catalyzed the reducing agent is anti-
Should.
Preferably, the catalyst is acidic materials.
Preferably, the catalyst is ammonium chloride or phosphoric acid.
Preferably, the quality of the reducing agent be 4 times of the graphene oxide quality and more than.
Preferably, the mass ratio of affiliated reducing agent and the catalyst is 1:1~10.
Preferably, the pollutant in the sewage includes pigment or heavy metal.
Preferably, the mass ratio of the graphene oxide and the pollutant is 0.5~2:1.
Preferably, the mass ratio 1 of the graphene oxide and the pollutant:1.
Preferably, the oxygenation efficiency of the graphene oxide is 100%.
Preferably, the preparation method of the graphene oxide comprises the following steps：
(1) preparation of graphite is pre-oxidized：With graphite powder as raw material, the concentrated sulfuric acid, manganese dioxide and five oxidations two are sequentially added
Phosphorus, is well mixed and reacts 2h~8h at 60 DEG C~100 DEG C, and stratification after cooling removes layer washing of precipitate to neutrality, dries
Obtain pre-oxidizing graphite；
(2) secondary oxidation of graphite is pre-oxidized：Under 0 DEG C of ice bath, by pre-oxidation graphite and the concentrated sulfuric acid obtained by step (1)
It is well mixed, add potassium permanganate, reaction successively to add secondary water and hydrogen peroxide under agitation after terminating, obtain golden yellow
The graphene oxide liquid mixture of color；
(3) cleaning of graphene oxide：The graphene oxide liquid mixture obtained with hydrochloric acid solution cleaning step (2), dialysis
Obtain gelatinous graphene oxide.
Preferably, step (1) described graphite powder is spectroscopically pure graphite powder.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show
Beneficial effect.
(1) present invention prepares graphene oxide (yield is 100%), graphite oxide based on Kovtyukhova methods are improved
Alkene carries out being related to add reducing agent, such as zinc powder, and catalyst ammonium chloride or phosphoric acid etc. nontoxic in in-situ reducing adsorption process
Property reagent realizes the efficient removal of pigment and heavy metal.
(2) pigment and heavy metal only need 5~10min to can reach close to 100% removal in this method treatment sewage, meet
Actual sewage processing requirement.
(3) this method is used to remove the pigment (dye of positive ion in water body：Methylene blue MB；Anionic dye：It is Congo red
CR, lemon yellow LY) and heavy metal ion (Cd2+,Pb2+), adsorption efficiency is respectively 99.57%, 99.95%, 98.46%,
99.92%th, 100% and adsorption capacity (MB, CR and Cd2+Meet Langmuir isotherm adsorption models, LY and Pb2+Meet
Freundlich isotherm adsorption models) it is respectively 2.6g g-1、7.6g g-1、3.2g g-1、8.4g g-1、17.9g g-1, it is and existing
Some adsorption technologies increase several times to hundred times compared to adsorption capacity.
(4) this method can simultaneously be processed and contain five kinds of water sample (MB, CR, LY, Cd of pollutant2+, Pb2+)；In addition it is a large amount of real
Border sample test (soil water sample, sanitary sewage etc.) also demonstrates that the method has good application prospect, practical and application
Scope is wide.
(5) present invention utilization metal simple-substance reducing agent, such as zinc powder in-situ reducing graphene oxide, can greatly increase stone
The adsorption efficiency and adsorption capacity of black alkene material.The method includes the pigment (dye of positive ion to multiple pollutant object：Methylene
Blue MB；Anionic dye：Congo red CR, lemon yellow LY) and heavy metal ion (Cd2+, Pb2+) pollutant adsorption efficiency approach
100%, the present invention for a kind of environmental protection and economy sewage disposal new method, can with it is green, supper-fast, efficiently removal water body in
Pigment, heavy metal and other pollutants.
Brief description of the drawings
Fig. 1 is different pigment (A.MB, B.CR, C.LY) the adsorption treatment pictures of embodiment 1 pair；
Fig. 2 is the SEM figures of each state of the adsorbent of sewage water treatment method adsorption process of the invention；
Fig. 3 is the phenogram of adsorption process adsorbent of the invention, and wherein A is the AFM of the GO that embodiment 1 is prepared
Figure；B and C are respectively the TEM figures and electron diffraction diagram of ZRGO；D, E, F are respectively the FTIR of GO and ZRGO, Raman and XRD；
Fig. 4 is the pigment of different initial concentrations and the adsorption efficiency of heavy metal ion and adsorption capacity figure；
Fig. 5 is soil muddy water (A. natural subsidences and B.ZRGO absorption comparison diagram:Each group is respectively from left to right treatment
0th, the design sketch after 10min, 5h, 24h and 7d)；
Fig. 6 is addition 5 kinds of pollutants (MB, CR, LY, Cd in soil muddy water2+, Pb2+) treatment effect figure；A groups are low dense
Degree 50mg L-1Water sample (A, A1 and A2 are respectively treatment 0, the design sketch after 10min and 24h) and B groups be high concentration 250mg
L-1Water sample (B, B1 and B2 are respectively treatment 0, the design sketch after 10min and 24h)；
Fig. 7 processes 10 minutes five kinds of adsorption efficiencies and adsorption capacity ratio of pollutant later for two kinds of concentration water samples of Fig. 6
Compared with block diagram.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each implementation method
Not constituting conflict each other can just be mutually combined.
The sewage water treatment method of the utilization reducing agent in-situ reducing graphene oxide that the present invention is provided, comprises the following steps：
Under agitation, graphene oxide, reducing agent and urge to being added in the sewage containing pigment or heavy metal or other pollutants
Agent；Reducing agent is used for in-situ reducing graphene oxide, and catalyst is used for the reduction reaction of catalytic reducer；Reducing agent is in catalysis
In the presence of agent, in-situ reducing graphene oxide, and pigment or heavy metal in absorption effluent, be can reach after 1~10 minute
Adsorption equilibrium, then separation of solid and liquid, solid phase is the black floccule precipitation containing pigment or heavy metal, and liquid phase is the dirt after treatment
Water.
Wherein, reducing agent is preferably the metal simple-substance that normal reduction potential is -2.5V~-0.4V (Vs.SHE), including magnesium
Powder, aluminium powder, zinc powder or iron powder, preferably zinc powder.
Catalyst is acidic materials, preferably ammonium chloride or phosphoric acid, and ammonium chloride effect is best.Sewage disposal side of the invention
Catalyst serves unexpected effect in method, and it provides sour environment, when metal simple-substance is used as reducing agent, due to urging
The presence of agent so that reactive gases hydrogen is generated in system, substantially reduces the time of adsorption equilibrium needs, at least shortens
It is more than half an hour.The catalyst of present invention selection not only acts as the effect for improving absorption water purification speed, nor can be to net
Water sample after change produces secondary pollution.
When processing the waste water containing pigment or heavy metal using the method for the present invention, the quality of the reducing agent for using is oxidation
4 times of Graphene quality and more than, the mass ratio of reducing agent and catalyst is 1:1~1:10, graphene oxide is dirty with sewage
The mass ratio for contaminating thing is 0.5~2:1, preferably 1:1, wherein pollutant includes pigment, heavy metal or other pollutants.
Graphene oxide is oxygenation efficiency close to or up 100% preferably using yield in sewage water treatment method of the invention
On the one hand graphene oxide, its purpose improves clean-up effect, is on the other hand to avoid introducing impurity, causes secondary pollution.Yield
Graphene oxide close to or up 100% can prepare graphene oxide (yield using based on improvement Kovtyukhova methods
For 100%), preparation method comprises the following steps：
(1) preparation of graphite is pre-oxidized：With graphite powder as raw material, it is preferred to use spectroscopically pure graphite powder, dense sulphur is sequentially added
Acid, manganese dioxide and phosphorus pentoxide, are well mixed and react 2h~8h at 60 DEG C~100 DEG C, and stratification after cooling is removed
Layer washing of precipitate is dried to obtain pre-oxidation graphite to neutrality；
(2) secondary oxidation of graphite is pre-oxidized：Under 0 DEG C of ice bath, by pre-oxidation graphite and the concentrated sulfuric acid obtained by step (1)
It is well mixed, add potassium permanganate, reaction successively to add secondary water and hydrogen peroxide under agitation after terminating, obtain golden yellow
The graphene oxide liquid mixture of color；
(3) cleaning of graphene oxide：The graphene oxide liquid mixture obtained with hydrochloric acid solution cleaning step (2), dialysis
Obtain gelatinous graphene oxide.
Specifically include following steps：
(1) preparation of graphite is pre-oxidized：With graphite powder as raw material (1~10g) (graphite powder is preferably spectroscopically pure graphite powder,
To prepare the graphene oxide that yield is 100%), sequentially add the concentrated sulfuric acid (5~50mL), manganese dioxide (0.5~15g)
With phosphorus pentoxide (1~10g), it is well mixed at 80 DEG C, makes its reaction 5h, after stopping heating, be cooled to room temperature, will be mixed
Thing is diluted to 400mL, stands overnight.Supernatant liquid is removed, filtering and washing on 0.22 μm of miillpore filter will be deposited in and, to neutrality, filtered
60 DEG C of drying about 6h of cake.
(2) secondary oxidation is further carried out to pre-oxidation graphite：Under 0 DEG C of ice-water bath, the graphite (first step that will be pre-oxidized
Product halves) it is placed in 20~46mL concentrated sulfuric acids and does not stop to stir.It is slow to add 2~10g potassium permanganate powders in batches
It is allowed to dissolve, adition process strict temperature control is below 10 DEG C.Then mixture reacts 4h at 35 DEG C.Add 100mL ice
In mixed solution, 48 DEG C of design temperature continues to stir 2h secondary water.300mL secondary water agitation and dilutions are added after the completion of reaction
Mixed solution.5~25mL hydrogenperoxide steam generators are added dropwise with vigorous stirring, now solution reaction acutely, shows golden yellow.Fill
Divide after stirring, stand overnight.
(3) cleaning of graphene oxide:Supernatant liquor is toppled over, remaining suspension is repeatedly clear with 10%HCl solution
Wash 6 times, 30min is stirred every time, then stand 30min, after being layered, remove supernatant liquor.After having washed, 600mL bis- is added
Secondary water, is stood, and then outwells supernatant, and remaining suspension is poured into bag filter is dialysed, and dialysis can obtain for seven days afterwards
Gelatinous graphene oxide, finally determines the concentration for having prepared graphene oxide.
Applicant of the present invention has been surprisingly found that, will be during reducing agent adds and carry out in graphene oxide in-situ reducing treatment sewage
Pigment or heavy metal, the adsorption efficiency and adsorption capacity of grapheme material, and time of equilibrium adsorption can be greatly increased
Greatly shorten, effect is more preferable after adding catalyst.It is several that general sorbent treatment dirt water pollutant reaches adsorption equilibrium needs
Even several days hour, pigment and heavy metal only need 5~10min to can reach close to 100% removal in this method treatment sewage, and
And common filtering can make separation of solid and liquid, meet actual sewage processing requirement.This method is used to remove pigment (cation in water body
Dyestuff：Methylene blue MB；Anionic dye：Congo red CR, lemon yellow LY) and heavy metal ion (Cd2+,Pb2+), adsorption efficiency
Respectively 99.57%, 99.95%, 98.46%, 99.92%, 100%；MB, CR, LY and Cd2+Adsorption capacity be respectively 2.6g
g-1、7.6g g-1、3.2g g-1、8.4g g-1、17.9g g-1, adsorption capacity increases several times compared with existing adsorption technology
To hundred times.
Represented using the Graphene adsorbent during zinc powder in-situ reducing graphene oxide with ZRGO in the present invention.
(ZRGO can represent whole in-situ reducing process, can also represent the Graphene during zinc powder in-situ reducing graphene oxide and inhale
Attached dose, the abbreviation ZRGO of Zinc-induced in situ Reduction of Graphene Oxide)
Of the invention is mainly water solubility using GO, and pigment and heavy metal ion in adsorbable water body, active force are electrostatic phase
Interaction and conjugation, after metallic reducing agent zinc powder to be added, graphene oxide can be reduced to Graphene (hydrophobicity thing
Matter) in-situ reducing sedimentation water purification is carried out, large stretch of graphene oxide is obtained containing a large amount of by zinc powder in-situ reducing in the process
The graphene oxide in activated adoption site, large stretch of graphene oxide is reunited during this in-situ reducing can wrap up pigment and weight
Metal ion, greatly increases the adsorption efficiency and adsorption capacity of adsorbent, adds acidic catalyst in adsorption process in situ herein
Agent, preferably ammonium chloride or phosphoric acid, catalyst provide sour environment, when metal simple-substance is used as reducing agent, due to catalyst
Presence so that reactive gases hydrogen is generated in system, substantially reduce adsorption equilibrium needs time, original position of the invention
Pollutant in reduction GO absorption effluents reaches adsorption equilibrium only needs 1~10min.
It is below embodiment：
Embodiment 1
A kind of method that utilization zinc powder in-situ reducing graphene oxide goes pigment and heavy metal ion in water removal, according to as follows
Step is carried out：
(1) graphene oxide in-situ reducing adsorpting pigment and heavy metal ion
A. the preparation of graphite is pre-oxidized：With spectroscopically pure graphite powder as raw material (2.4g), the concentrated sulfuric acid (10mL), two are sequentially added
Manganese oxide (2g) and phosphorus pentoxide (2g), are well mixed at 80 DEG C, make its reaction 5h, after stopping heating, are cooled to room temperature,
Mixture is diluted to 400mL, is stood overnight.Supernatant liquid is removed, filtering and washing will be deposited on 0.22 μm of miillpore filter extremely
Neutrality, 60 DEG C of drying about 6h of filter cake.
B. secondary oxidation is further carried out to pre-oxidation graphite：Under 0 DEG C of ice-water bath, the graphite (first step that will be pre-oxidized
Product halves) it is placed in the 46mL concentrated sulfuric acids and does not stop to stir.It is slow to add 6g potassium permanganate powders to be allowed to dissolve in batches,
Adition process strict temperature control is below 10 DEG C.Then mixture reacts 4h at 35 DEG C.100mL ice secondary water is added in mixed
Close in solution, 48 DEG C of design temperature continues to stir 2h.300mL secondary water agitation and dilution mixed solutions are added after the completion of reaction.
Lower dropwise addition 10mL hydrogenperoxide steam generators are stirred vigorously, now solution reaction acutely, shows golden yellow.After stirring,
Stand overnight.
C. the cleaning of graphene oxide:Supernatant liquor is toppled over, remaining suspension is cleaned repeatedly with 10%HCl solution
6 times, 30min is stirred every time, then stand 30min, after being layered, remove supernatant liquor.After having washed, 600mL is added bis- times
Water, is stood, and then outwells supernatant, and remaining suspension is poured into bag filter is dialysed, and dialysis can be coagulated for seven days afterwards
Gluey graphene oxide, finally determines the concentration for having prepared graphene oxide, and concentration is 5mg/mL, and yield is 100%.
D. 250mg L are respectively in pigment MB, CR and LY-1, heavy metal ion Cd2+And Pb2+Respectively 250mg L-1Five
The graphene oxide that 2.5mg steps c is prepared, wherein MB, CR, LY, Cd are separately added into part water sample2+And Pb2+Quality with
The mass ratio of graphene oxide is 1:1.Magnetic agitation is well mixed, and immediately adds 20mg zinc powders and 160mg ammonium chlorides,
Adsorption equilibrium is can reach after isothermal adsorption 10min under high speed magnetic agitation, black floccule precipitation is filtered to remove, obtained
Five parts of solution are used for its adsorption efficiency of quantitative measurment and adsorption capacity.Can with ultraviolet-visible spectrophotometry measure sewage disposal it
Afterwards after the residual volume of pigment and Atomic Absorption Spectrometry amount sewage disposal heavy metal residual volume (wherein, MB, CR and LY's
Maximum absorption wavelength is respectively 664nm, 488nm, 426nm；Cd2+And Pb2+Analytical line is respectively 228.80nm, 216.70nm).
Wherein, C0(mg mL-1) and Ce(mg mL-1) be various pollutants initial concentration and equilibrium concentration, V (mL) is molten
Liquid cumulative volume, m (g) is total consumption of adsorbent.
Through analysis, the present embodiment utilizes zinc powder in-situ reducing graphene oxide, the adsorbent to be defined as ZRGO.According to implementation
The method of example 1, five kinds of pollutants are processed respectively, according to pollutant (pigment MB, CR and LY, heavy metal Cd2+And Pb2+) and oxidation
Graphene mass ratio is from 1:1 to 10:1 adsorption treatment, is increasing the amount of pollutant always, until the fully saturated fitting side of absorption
Journey obtains respective maximum adsorption capacity.Analysis obtains ZRGO to the adsorption efficiency of various pollutants, adsorption capacity and corresponding
Fitting parameter be shown in Table 1.
Table 1ZRGO adsorpting pigments (MB, CR, LY) and heavy metal ion (Cd2+, Pb2+) on Langmuir and
Freundlich model fitting parameters
From various Langmuir and Freundlich model fitting parameters in table 1, zinc powder in-situ reducing of the invention
The ZRGO adsorbents of graphene oxide are to MB, CR, LY, Cd2+And Pb2+Adsorption capacity is respectively 2.6g g-1、7.6g g-1、3.2g
g-1、8.4g g-1、17.9g g-1, the adsorption capacity to pollutant compared with existing adsorption technology increases several times to hundreds of
Times.It is fitted by linear equation and obtains corresponding coefficient correlation, MB, CR and Cd2+Meet Langmuir isotherm adsorption models,
LY and Pb2+Meet Freundlich isotherm adsorption models.
Fig. 1 is different pigment (A.MB, B.CR, C.LY) the adsorption treatment pictures of embodiment 1 pair, A in Fig. 11、B1、C1Not locate
Three kinds of pigment solutions of reason；A2、B2、C2After respectively adding graphene oxide, there is no significant change (absorption effect in three kinds of solution
Fruit is not apparent)；A3、B3、C3After continuously adding zinc powder, discovery has floccule to precipitate generation, and solution colour is slightly more shallow；A4、
B4、C4After adding acidic catalyst ammonium chloride or phosphoric acid, substantial amounts of black floccule is produced, reunion sedimentation phenomenon occurs at once,
After the adsorbed sedimentation of pigment solution, colourless transparent solution is obtained.Whole adsorption equilibrium process can be supper-fast complete within 10min
Into.
Fig. 2 is the SEM figures of each state of adsorbent in adsorption process.A is the graphene oxide of lamellar structure in Fig. 2；B
For the reduced graphene that graphene oxide addition zinc powder reduction is obtained；C is that graphene oxide adds zinc powder and acidic catalyst chlorine
Change the reduced graphene that ammonium reduction is obtained；D excessive zinc powder and ammonium chloride reduced graphene for C is washed away.Inhaled by adsorption process
The SEM figures of attached dose of each state understand that in in-situ reducing adsorption process of the present invention, large stretch of graphene oxide is in zinc powder and chlorine
Change generation in-situ reducing agglomeration under conditions of ammonium, substantial amounts of activated adoption site is generated in this situ process, greatly
Increase its adsorption efficiency and adsorption capacity.
Fig. 3 A are the AFM figures of the GO that embodiment 1 is prepared；B and C is the TEM figures and electron diffraction diagram of ZRGO；D、E、F
For the FTIR of GO and ZRGO, Raman and XRD.A, B, C figure prove that large stretch of graphene oxide occurs in-situ reducing and obtains reducing stone
There is agglomeration (producing more activated adoption sites) in black alkene, its lamellar structure, advantageously in absorption Water treatment；D、
E, F are FTIR, Raman, the XRD of GO and ZRGO, and as above shown in collection of illustrative plates, graphene oxide is under conditions of zinc powder and ammonium chloride
In-situ reducing is carried out, successfully becomes redox graphene.
Fig. 4 is the pigment of different initial concentrations and the adsorption efficiency of heavy metal ion and adsorption capacity figure.Fig. 4 has inquired into this
The relation of adsorption efficiency and adsorption capacity in invention in-situ reducing adsorption process and the initial concentration of various pollutants.Such as Fig. 4
Understand, with the increase of pollutant concentration, its adsorption efficiency and adsorption capacity are also gradually increasing, and finally reach saturation absorption flat
Weighing apparatus.
Embodiment 2
The method that the graphene oxide and in-situ reducing graphene oxide that embodiment 1 is prepared process sewage, uses
In soil muddy water treatment and contrasted with the natural subsidence of soil muddy water, (A groups are naturally heavy to Fig. 5 soil muddy water
Drop；B groups are that ZRGO adsorbs comparison diagram, and each group is respectively the design sketch after treatment 0,10min, 5h, 24h and 7d from left to right).
It can be seen that B group graphene oxide in-situ reducing adsorption treatment soil muddy water processes, 10min is that to can reach purifying water effect (right
Than natural subsidence process).
Embodiment 3
Simulation actual sewage water sample, five kinds of pollutants (MB, CR, LY, Cd are added in soil muddy water2+, Pb2+), and be configured to
Two kinds of different concentration, 50mg L-1With 250mg L-1Two groups, the graphene oxide prepared using embodiment 1, according to oxygen
Graphite alkene and pollutant mass ratio are 1:1, catalyst is ammonium chloride, and reducing agent is the quality of zinc powder, zinc powder and ammonium chloride
Than being 1:3, the mass ratio of graphene oxide and zinc powder is 1:8, test the clean-up effect of the method.
5 kinds of pollutants (MB, CR, LY, Cd are added in Fig. 6 soil muddy waters2+, Pb2+) treatment effect figure；A groups are low concentration
50mg L-1Water sample (A, A1 and A2 are respectively treatment 0, the design sketch after 10min and 24h) and B groups be high concentration 250mg L-1
Water sample (B, B1 and B2 are respectively treatment 0, the design sketch after 10min and 24h).
Fig. 7 processes 10 minutes five kinds of adsorption efficiencies and adsorption capacity ratio of pollutant later for two kinds of concentration water samples of Fig. 6
Compared with block diagram, wherein (a) and (b) is respectively the adsorption efficiency of each pollutant and absorption after low concentration group in Fig. 6 is processed 10 minutes
Capacity block diagram；C () and (d) is respectively the adsorption efficiency of each pollutant and absorption after Fig. 6 middle and high concentrations group is processed 10 minutes and holds
Amount block diagram.
It is colourless transparent solution that Fig. 6 and Fig. 7 display sewage samples are cleaned, and histogram data analysis shows the adsorption process pair
High density pollution thing processes its adsorption efficiency and adsorption capacity is above processing low concentration pollutant, and the sample treatment of simulation sewage is only needed
10min is that can reach adsorption equilibrium.
In low concentration (50mg mL-1) pollutant process five kinds of pollutants (MB, CR, LY, Cd2+, Pb2+) adsorption efficiency and suction
Attached capacity distinguishes 99.53% and 994.48mg g-1, 89.65% and 895.75mg g-1, 89.88% and 898.09mg g-1,
95.85% and 957.76mg g-1, 99.36% and 992.77mg g-1；In high concentration (250mg mL-1) five kinds of pollutant process
Pollutant (MB, CR, LY, Cd2+, Pb2+) adsorption efficiency and adsorption capacity distinguish 99.78% and 998.63mg g-1, 99.40% He
994.80mg g-1, 99.30% and 993.77mg g-1, 96.73% and 968.11mg g-1, 99.85% and 999.34mg g-1,
The sample treatment of simulation sewage only needs 10 minutes to can reach adsorption equilibrium.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include
Within protection scope of the present invention.
Claims (10)
1. a kind of sewage water treatment method of utilization reducing agent in-situ reducing graphene oxide, it is characterised in that under agitation,
To graphene oxide and reducing agent, separation of solid and liquid is added in sewage, gained liquid phase is the sewage after treatment；The reducing agent is used for
In-situ reducing graphene oxide.
2. sewage water treatment method as claimed in claim 1, it is characterised in that the reducing agent be normal reduction potential for-
At least one in the metal simple-substance of 2.5V~-0.4V, preferably magnesium powder, aluminium powder, zinc powder and iron powder, more preferably zinc
Powder.
3. sewage water treatment method as claimed in claim 1, it is characterised in that catalyst has been additionally added in the sewage, it is described
Catalyst is used to be catalyzed the reduction reaction of the reducing agent.
4. sewage water treatment method as claimed in claim 3, it is characterised in that the catalyst is acidic materials, the catalysis
Agent is preferably ammonium chloride or phosphoric acid.
5. sewage water treatment method as claimed in claim 1, it is characterised in that the quality of the reducing agent is the graphite oxide
4 times of alkene quality and more than.
6. sewage water treatment method as claimed in claim 4, it is characterised in that the mass ratio of affiliated reducing agent and the catalyst
It is 1:1~10.
7. sewage water treatment method as claimed in claim 1, it is characterised in that the pollutant in the sewage includes pigment or weight
Metal.
8. sewage water treatment method as claimed in claim 7, it is characterised in that the matter of the graphene oxide and the pollutant
Amount is than being 0.5~2:1, preferably 1:1.
9. sewage water treatment method as claimed in claim 1, it is characterised in that the oxygenation efficiency of the graphene oxide is 100%.
10. sewage water treatment method as claimed in claim 9, it is characterised in that the preparation method of the graphene oxide includes
Following steps：
(1) preparation of graphite is pre-oxidized：With graphite powder as raw material, preferably spectroscopically pure graphite powder sequentially adds the concentrated sulfuric acid, dioxy
Change manganese and phosphorus pentoxide, be well mixed and react 2h~8h at 60 DEG C~100 DEG C, stratification after cooling takes lower sediment
Washing is dried to obtain pre-oxidation graphite to neutrality；
(2) secondary oxidation of graphite is pre-oxidized：Under 0 DEG C of ice bath, the pre-oxidation graphite obtained by step (1) is mixed with the concentrated sulfuric acid
Uniformly, add potassium permanganate, reaction successively to add secondary water and hydrogen peroxide under agitation after terminating, obtain golden yellow
Graphene oxide liquid mixture；
(3) cleaning of graphene oxide：The graphene oxide liquid mixture obtained with hydrochloric acid solution cleaning step (2), dialysis is obtained
Gelatinous graphene oxide.
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| CN107308826A (en) * | 2017-07-06 | 2017-11-03 | 浙江大学 | A kind of preparation method and application of graphene oxide seperation film |
| CN109705230A (en) * | 2018-12-24 | 2019-05-03 | 江苏辰星药业股份有限公司 | A kind of method and carragheen for extracting carragheen from red algae |
| CN110437595A (en) * | 2018-05-03 | 2019-11-12 | 华中科技大学 | A kind of antistatic biodegradable polymers composite material and preparation method |
| CN110642323A (en) * | 2018-06-26 | 2020-01-03 | 北京大学 | Method for initiating graphene oxide to controllably release organic compound by using reducing agent |
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| CN102557013A (en) * | 2010-12-28 | 2012-07-11 | 国家纳米科学中心 | Preparation method for reduced graphene oxide |
| EP3013742A1 (en) * | 2013-06-25 | 2016-05-04 | Council of Scientific & Industrial Research An Indian registered body incorporated under the Registration of Societies Act (Act XXI of 1860) | Reduced graphene oxide-silver phosphate (rgo-agp) and a process for the preparation thereof for the photodegradation of organic dyes |
| CN106268642A (en) * | 2016-09-09 | 2017-01-04 | 北京优碳环能科技有限公司 | Bobbles shape zinc oxide/graphene composite adsorbent and preparation method and application |
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| EP3013742A1 (en) * | 2013-06-25 | 2016-05-04 | Council of Scientific & Industrial Research An Indian registered body incorporated under the Registration of Societies Act (Act XXI of 1860) | Reduced graphene oxide-silver phosphate (rgo-agp) and a process for the preparation thereof for the photodegradation of organic dyes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107308826A (en) * | 2017-07-06 | 2017-11-03 | 浙江大学 | A kind of preparation method and application of graphene oxide seperation film |
| CN110437595A (en) * | 2018-05-03 | 2019-11-12 | 华中科技大学 | A kind of antistatic biodegradable polymers composite material and preparation method |
| CN110642323A (en) * | 2018-06-26 | 2020-01-03 | 北京大学 | Method for initiating graphene oxide to controllably release organic compound by using reducing agent |
| CN110642323B (en) * | 2018-06-26 | 2021-07-27 | 北京大学 | Method for initiating graphene oxide to controllably release organic compound by using reducing agent |
| CN109705230A (en) * | 2018-12-24 | 2019-05-03 | 江苏辰星药业股份有限公司 | A kind of method and carragheen for extracting carragheen from red algae |
| CN109705230B (en) * | 2018-12-24 | 2021-04-09 | 江苏辰星药业股份有限公司 | Method for extracting carrageenan from red algae and carrageenan |
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