CN106745463B - A kind of sewage water treatment method using reducing agent in-situ reducing graphene oxide - Google Patents
A kind of sewage water treatment method using reducing agent in-situ reducing graphene oxide Download PDFInfo
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- CN106745463B CN106745463B CN201710048173.4A CN201710048173A CN106745463B CN 106745463 B CN106745463 B CN 106745463B CN 201710048173 A CN201710048173 A CN 201710048173A CN 106745463 B CN106745463 B CN 106745463B
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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
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Abstract
The invention discloses a kind of high-efficiency sewage processing methods using metal simple-substance reducing agent in-situ reducing graphene oxide, its object is to by when graphene oxide handles sewage, reducing agent and catalyst is added, in-situ reducing graphene oxide greatly increases graphene to the adsorption efficiency and adsorption capacity of dirty water pollutant.This method includes the pigment (dye of positive ion: methylene blue MB to multiple pollutant object；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 the prior art.The present invention is a kind of sewage treatment new method of environmental protection and economy, can it is green, supper-fast, efficiently remove pigment, heavy metal or other pollutants in water body.
Description
Technical field
The invention belongs to water body purification and environmental protection technical fields, more particularly, to a kind of in situ using reducing agent
The sewage water treatment method of redox graphene.
Background technique
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
It is often coexisted in water body environment with heavy metal, these environmental contaminants have high toxicity, and carcinogenicity and easily exists at non-biodegradable
The harm such as enrichment, causes huge harm to human health and environment in organism.In view of this harm seriousness and
Chronicity, government has formulated stringent standard to the green harmless treatment of the waste water containing pigment and heavy metal, therefore is discharging
These pollutants must be removed before sewage.Purifying pigment and heavy metal ion polluted-water, there are many method, such as chemistry are heavy
The methods of 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 current main active charcoal of adsorbent, metal oxide, functional silica gel and oxygen
Graphite alkene and graphene-based material etc., therefore adsorption treatment on sewage has both the adsorbent of multiple types, it is efficiently, easily separated, it is easy to
The advantages that operation and lower cost.Graphene oxide and graphite alkenyl nanometer materials have special two-dimensional structure, various
The characteristics such as oxygen-containing functional group and great specific surface area are optimal candidate materials in adsorbent.But existing graphene material
Sewage treatment method is expected there are costly, and time-consuming, and processing pollutant object is single, and the disadvantages of easily cause secondary pollution.
Therefore, how economical and eco-friendly, quickly and efficiently simultaneously remove pigment and metal ion in sewage be still the mankind concern hot spot
Problem.
Based on graphene oxide, pigment and heavy metal ion have preferable absorption property in processing sewage, it has been found that
Can use zinc powder in-situ reducing graphene oxide can greatly increase adsorption efficiency and adsorption capacity.This work disposal is more
Kind pollutant object includes the pigment (dye of positive ion: methylene blue MB；Anionic dye: Congo red CR, lemon yellow LY) and again
Metal ion (Cd2+,Pb2+), this method is to the adsorption efficiencies of these pollutants close to 100%.We have developed a kind of environmental protection warp
The sewage treatment new method of Ji, can be green, supper-fast, efficiently removes pigment and heavy metal in water body.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, it is former using metal simple-substance reducing agent that the present invention provides a kind of
The high-efficiency sewage processing method of position redox graphene, its object is to by being added when graphene oxide handles sewage
Reducing agent and catalyst, in-situ reducing graphene oxide, greatly increase graphene to the adsorption efficiency of dirty water pollutant and
Adsorption capacity, thus the solution prior art is low using grapheme material processing sewage adsorption capacity, adsorption efficiency is low, time-consuming
The technical issues of.
To achieve the above object, according to one aspect of the present invention, a kind of utilization reducing agent in-situ reducing oxidation is provided
Graphene oxide and reducing agent are added into sewage under agitation for the sewage water treatment method of graphene, are separated by solid-liquid separation, institute
Liquid phase is treated sewage；The reducing agent is used for in-situ reducing graphene oxide.
Preferably, it is -2.5V~-0.4V metal simple-substance that the reducing agent, which is normal reduction potential,.
Preferably, the reducing agent is at least one of 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-
It answers.
Preferably, the catalyst is acidic materials.
Preferably, the catalyst is ammonium chloride or phosphoric acid.
Preferably, the quality of the reducing agent is 4 times or more of the graphene oxide quality.
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 1:1 of the graphene oxide and the pollutant.
Preferably, the oxygenation efficiency of the graphene oxide is 100%.
Preferably, the preparation method of the graphene oxide includes the following steps:
(1) it pre-oxidizes the preparation of graphite: using graphite powder as raw material, sequentially adding the concentrated sulfuric acid, manganese dioxide and five oxidations two
Phosphorus, is uniformly mixed and in 60 DEG C~100 DEG C reaction 2h~8h, it is cooling after stratification, take lower layer's washing of precipitate to neutrality, dry
Obtain pre-oxidation graphite；
(2) secondary oxidation of graphite is pre-oxidized: under 0 DEG C of ice bath, by the resulting pre-oxidation graphite of step (1) and the concentrated sulfuric acid
It is uniformly mixed, potassium permanganate is added, secondary water and hydrogen peroxide is successively added under agitation after reaction, obtains 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) graphite powder is spectroscopically pure graphite powder.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect.
(1) the present invention is based on improve Kovtyukhova method to prepare graphene oxide (yield 100%), graphite oxide
Alkene carries out that reducing agent is added involved in in-situ reducing adsorption process, for example zinc powder and catalyst ammonium chloride or phosphoric acid etc. are nontoxic
Property reagent realizes the efficient removal of pigment and heavy metal.
(2) pigment and heavy metal only need 5~10min i.e. and can reach to remove close to 100% in this method processing sewage, satisfaction
Actual sewage processing requirement.
(3) this method is used to remove (the dye of positive ion: methylene blue MB of pigment in water body；Anionic dye: Congo red
CR, lemon yellow LY) and heavy metal ion (Cd2+,Pb2+), adsorption efficiency is respectively 99.57%, 99.95%, 98.46%,
99.92%, 100% and adsorption capacity (MB, CR and Cd2+Meet Langmuir isotherm adsorption model, LY and Pb2+Meet
Freundlich isotherm adsorption model) it is respectively 2.6g g-1、7.6g g-1、3.2g g-1、8.4g g-1、17.9g g-1, and it is existing
Some adsorption technologies increase several times to hundred times compared to adsorption capacity.
(4) this method can be handled simultaneously containing there are five types of water sample (MB, CR, LY, the Cd of pollutant2+, Pb2+)；Furthermore a large amount of real
Border sample test (soil water sample, sanitary sewage etc.) also turns out that this method has good application prospect, practical and application
Range is wide.
(5) present invention can greatly increase stone such as zinc powder in-situ reducing graphene oxide using metal simple-substance reducing agent
The adsorption efficiency and adsorption capacity of black alkene material.This method includes the pigment (dye of positive ion: methylene to multiple pollutant object
Blue MB；Anionic dye: Congo red CR, lemon yellow LY) and heavy metal ion (Cd2+, Pb2+) pollutant adsorption efficiency it is close
100%, the present invention be a kind of environmental protection and economy sewage treatment new method, can it is green, supper-fast, efficiently remove in water body
Pigment, heavy metal and other pollutants.
Detailed description of the invention
Fig. 1 is 1 pair of embodiment different pigment (A.MB, B.CR, C.LY) adsorption treatment pictures；
Fig. 2 is the SEM figure of each state of 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 for the GO that embodiment 1 is prepared
Figure；B and C is respectively the TEM figure and electron diffraction diagram of ZRGO；D, E, F are respectively the FTIR of GO and ZRGO, Raman and XRD diagram；
Fig. 4 is the pigment of different initial concentrations and the adsorption efficiency of heavy metal ion and adsorption capacity figure；
Fig. 5 is that (A. natural subsidence and B.ZRGO absorption comparison diagram: each group is processing respectively from left to right to soil muddy water
0,10min, 5h, for 24 hours with the effect picture after 7d)；
Fig. 6 is 5 kinds of pollutants (MB, CR, LY, Cd of addition in soil muddy water2+, Pb2+) treatment effect figure；A group is low dense
Spend 50mg L-1Water sample (A, A1 and A2 be respectively handle 0,10min and for 24 hours after effect picture) and B group be high concentration 250mg
L-1Water sample (B, B1 and B2 be respectively handle 0,10min and for 24 hours after effect picture)；
The adsorption efficiency and adsorption capacity ratio of five kinds of pollutants after two kinds of concentration water samples that Fig. 7 is Fig. 6 are handled 10 minutes
Compared with histogram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
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 in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Sewage water treatment method provided by the invention using reducing agent in-situ reducing graphene oxide, includes the following steps:
Under agitation, graphene oxide, reducing agent are added in the sewage of Xiang Hanyou pigment or heavy metal or other pollutants and urges
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 being catalyzed
Under the action of agent, in-situ reducing graphene oxide, and pigment or heavy metal in absorption effluent, 1~can reach after ten minutes
Then adsorption equilibrium is separated by solid-liquid separation, solid phase is to precipitate containing the black floccule of pigment or heavy metal, and liquid phase is dirty for treated
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 treatment side of the invention
Catalyst plays the role of unexpected in method, provides acidic environment, when metal simple-substance is as reducing agent, due to urging
The presence of agent substantially reduces the time of adsorption equilibrium needs, at least shortens so that producing reactive gases hydrogen in system
It is more than half an hour.The catalyst that the present invention selects not only acts as the effect for improving absorption water purification rate, nor can be to net
Water sample after change generates secondary pollution.
When handling the waste water containing pigment or heavy metal using method of the invention, the quality of the reducing agent used is oxidation
The mass ratio of 4 times or more of graphene quality, reducing agent and catalyst is 1:1~1:10, dirt in graphene oxide and sewage
The mass ratio for contaminating object is 0.5~2:1, preferably 1:1, and wherein pollutant includes pigment, heavy metal or other pollutants.
Graphene oxide preferably uses yield i.e. oxygenation efficiency to be close to or up to 100% in sewage water treatment method of the invention
On the one hand graphene oxide, purpose improve clean-up effect, be on the other hand to avoid introducing impurity, cause secondary pollution.Yield
Graphene oxide (yield can be prepared using based on improvement Kovtyukhova method by being close to or up to 100% graphene oxide
For 100%), preparation method includes the following steps:
(1) preparation of graphite is pre-oxidized: using graphite powder as raw material, it is preferred to use spectroscopically pure graphite powder sequentially adds dense sulphur
Acid, manganese dioxide and phosphorus pentoxide, are uniformly mixed and in 60 DEG C~100 DEG C reaction 2h~8h, and stratification after cooling down 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 the resulting pre-oxidation graphite of step (1) and the concentrated sulfuric acid
It is uniformly mixed, potassium permanganate is added, secondary water and hydrogen peroxide is successively added under agitation after reaction, obtains 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 comprise the following steps:
(1) pre-oxidize graphite preparation: using graphite powder as raw material (1~10g) (graphite powder is preferably spectroscopically pure graphite powder,
The graphene oxide that yield is 100% is prepared), sequentially add the concentrated sulfuric acid (5~50mL), manganese dioxide (0.5~15g)
It with phosphorus pentoxide (1~10g), is uniformly mixed at 80 DEG C, it is made to react 5h, after stopping heating, be cooled to room temperature, will mix
Object 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 filtered to neutrality
60 DEG C of drying about 6h of cake.
(2) to pre-oxidation graphite further progress secondary oxidation: under 0 DEG C of ice-water bath, by the graphite (first step of pre-oxidation
Product halves) it is placed in 20~46mL concentrated sulfuric acid and does not stop to stir evenly.2~10g potassium permanganate powder is slowly added in batches
It is allowed to dissolve, adition process strict temperature control is at 10 DEG C or less.Then mixture reacts 4h at 35 DEG C.100mL ice is added
Secondary water is in mixed solution, 48 DEG C of set temperature, continues to stir 2h.300mL secondary water agitation and dilution is added after the reaction was completed
Mixed solution.5~25mL hydrogenperoxide steam generator is added dropwise with vigorous stirring, solution reaction is violent at this time, shows golden yellow.It fills
Divide after mixing evenly, stands overnight.
(3) cleaning of graphene oxide: supernatant liquor is toppled over, and remaining suspension is repeatedly clear with 10%HCl solution
It washes 6 times, stirs 30min every time, be then allowed to stand 30min, after being layered, remove supernatant liquor.After having washed, 600mL bis- is added
Secondary water stands, then outwells supernatant, and remaining suspension, which pours into bag filter, dialyses, and after dialysis seven days, can be obtained
Gelatinous graphene oxide finally measures the concentration for having prepared graphene oxide.
Applicant of the present invention has been surprisingly found that, reducing agent is added in graphene oxide and is carried out in in-situ reducing processing sewage
Pigment or heavy metal, the adsorption efficiency and adsorption capacity of grapheme material, and time of equilibrium adsorption can be greatly increased
It greatly shortens, effect is more preferable after catalyst is added.It is several that the general dirty water pollutant of adsorbent processing reaches adsorption equilibrium needs
Hours even several days, pigment and heavy metal, which only need 5~10min i.e., in this method processing sewage can reach close to 100% removal, and
And common filtering can make to be separated by solid-liquid separation, and meet actual sewage processing requirement.This method is for removing (the cation of pigment 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.
It is indicated with ZRGO using the graphene adsorbent during zinc powder in-situ reducing graphene oxide in the present invention.
(ZRGO can indicate entire in-situ reducing process, can also represent the graphene suction during zinc powder in-situ reducing graphene oxide
Attached dose, the abbreviation ZRGO of Zinc-induced in situ Reduction of Graphene Oxide)
The present invention mainly utilizes GO for water solubility, 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 object
Matter) in-situ reducing sedimentation water purification is carried out, large stretch of graphene oxide is obtained by zinc powder in-situ reducing containing a large amount of in the process
The graphene oxide in activated adoption site, the reunion of large stretch of graphene oxide can wrap up pigment and again during this in-situ reducing
Metal ion greatly increases the adsorption efficiency and adsorption capacity of adsorbent, and acidic catalyst is added in adsorption process in situ herein
Agent, preferably ammonium chloride or phosphoric acid, catalyst provide acidic environment, when metal simple-substance is as reducing agent, due to catalyst
Presence substantially reduce the time of adsorption equilibrium needs, original position of the invention so that produce reactive gases hydrogen in system
Pollutant in reduction GO absorption effluent, which reaches adsorption equilibrium, only needs 1~10min.
The following are embodiments:
Embodiment 1
A method of pigment and heavy metal ion in water removal being gone using zinc powder in-situ reducing graphene oxide, according to as follows
Step carries out:
(1) graphene oxide in-situ reducing adsorpting pigment and heavy metal ion
A. it pre-oxidizes the preparation of graphite: using spectroscopically pure graphite powder as raw material (2.4g), sequentially adding the concentrated sulfuric acid (10mL), two
Manganese oxide (2g) and phosphorus pentoxide (2g) are uniformly mixed at 80 DEG C, it is made to react 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. to pre-oxidation graphite further progress secondary oxidation: under 0 DEG C of ice-water bath, by the graphite (first step of pre-oxidation
Product halves) it is placed in the 46mL concentrated sulfuric acid and does not stop to stir evenly.6g potassium permanganate powder is slowly added in batches to be allowed to dissolve,
Adition process strict temperature control is at 10 DEG C or less.Then mixture reacts 4h at 35 DEG C.100mL ice secondary water is added in mixed
It closes in solution, 48 DEG C of set temperature, continues to stir 2h.300mL secondary water agitation and dilution mixed solution is added after the reaction was completed.?
It is vigorously stirred lower dropwise addition 10mL hydrogenperoxide steam generator, solution reaction is violent at this time, shows golden yellow.After stirring,
It stands overnight.
C. the cleaning of graphene oxide: supernatant liquor is toppled over, and remaining suspension is cleaned repeatedly with 10%HCl solution
6 times, 30min is stirred every time, is then allowed to stand 30min, after being layered, removes supernatant liquor.After having washed, it is added 600mL bis- times
Water stands, then outwells supernatant, and remaining suspension, which pours into bag filter, dialyses, and after dialysis seven days, can be coagulated
Gelatinous graphene oxide finally measures the concentration for having prepared graphene oxide, concentration 5mg/mL, yield 100%.
It d. is respectively 250mg L in pigment MB, CR and LY-1, heavy metal ion Cd2+And Pb2+Respectively 250mg L-1Five
It is separately added into the graphene oxide that 2.5mg step c is prepared in part water sample, wherein MB, CR, LY, Cd2+And Pb2+Quality with
The mass ratio of graphene oxide is 1:1.Magnetic agitation is uniformly mixed, and 20mg zinc powder and 160mg ammonium chloride is immediately added,
It can reach adsorption equilibrium after isothermal adsorption 10min under high speed magnetic agitation, be filtered to remove black floccule precipitating, obtain
Five parts of solution are used for its adsorption efficiency of quantitative measurment and adsorption capacity.Can with ultraviolet-visible spectrophotometry measure sewage treatment it
Afterwards after the residual volume of pigment and Atomic Absorption Spectrometry amount sewage treatment 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 total volume, m (g) are total dosages of adsorbent.
Through analyzing, the present embodiment utilizes zinc powder in-situ reducing graphene oxide, which is defined as ZRGO.According to implementation
The method of example 1, five kinds of pollutants are handled respectively, according to pollutant (pigment MB, CR and LY, heavy metal Cd2+And Pb2+) and oxidation
Graphene mass ratio adsorption treatment from 1:1 to 10:1, is increasing always the amount of pollutant, until adsorbing fully saturated fitting side
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 pigment (MB, CR, LY) and heavy metal ion (Cd2+, Pb2+) about Langmuir and
Freundlich model fitting parameter
By Langmuir and Freundlich model fitting parameters various in table 1 it is found that zinc powder in-situ reducing of the invention
The ZRGO adsorbent of graphene oxide is 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, several times are increased to several hundred to the adsorption capacity of pollutant compared with existing adsorption technology
Times.It is fitted to obtain corresponding related coefficient it is found that MB, CR and Cd by linear equation2+Meet Langmuir isotherm adsorption model,
LY and Pb2+Meet Freundlich isotherm adsorption model.
Fig. 1 is 1 pair of embodiment different pigment (A.MB, B.CR, C.LY) adsorption treatment pictures, A in Fig. 11、B1、C1Not locate
Three kinds of pigment solutions of reason；A2、B2、C2After graphene oxide respectively is added, significant change (absorption effect does not occur for three kinds of solution
Fruit is not apparent)；A3、B3、C3After continuously adding zinc powder, discovery has floccule precipitating to generate, and solution colour is slightly shallow；A4、
B4、C4After acidic catalyst ammonium chloride or phosphoric acid is added, a large amount of black floccule is generated, reunion sedimentation phenomenon immediately occurred,
After pigment solution is adsorbed sedimentation, colourless transparent solution is obtained.Entire adsorption equilibrium process can be supper-fast complete within 10min
At.
Fig. 2 is the SEM figure of each state of adsorbent in adsorption process.A is the graphene oxide of lamellar structure in Fig. 2；B
The reduced graphene that zinc powder reduction obtains is added for graphene oxide；C is that zinc powder and acidic catalyst chlorine is added in graphene oxide
Change the reduced graphene that ammonium restores；D is that C washes away excessive zinc powder and ammonium chloride reduced graphene.By being inhaled in adsorption process
The SEM of attached dose of each state schemes it is found that in in-situ reducing adsorption process of the present invention, and large stretch of graphene oxide is in zinc powder and chlorine
In-situ reducing agglomeration occurs under conditions of change ammonium, produces a large amount of activated adoption site in this situ process, greatly
Increase its adsorption efficiency and adsorption capacity.
The AFM figure that Fig. 3 A is the GO that embodiment 1 is prepared；The TEM figure and electron diffraction diagram that B and C is ZRGO；D,E,F
For the FTIR of GO and ZRGO, Raman and XRD diagram.A, B, C figure prove that large stretch of graphene oxide occurs in-situ reducing and obtains reduction stone
Agglomeration (generating more activated adoption sites) occurs for black alkene, lamellar structure, is more conducive to absorption water purification process；D,
E, F is FTIR, Raman of GO and ZRGO, XRD diagram, and shown in map as above, graphene oxide is under conditions of zinc powder and ammonium chloride
In-situ reducing is carried out, redox graphene is successfully become.
Fig. 4 is the pigment of different initial concentrations and the adsorption efficiency and adsorption capacity figure of heavy metal ion.Fig. 4 has inquired into this
The relationship of the initial concentration of adsorption efficiency and adsorption capacity and various pollutants in invention in-situ reducing adsorption process.Such as Fig. 4
It is found that adsorption efficiency and adsorption capacity are also being gradually increased with the increase of pollutant concentration, it is flat to finally reach saturation absorption
Weighing apparatus.
Embodiment 2
The method for graphene oxide and in-situ reducing graphene oxide the processing sewage that embodiment 1 is prepared, is used
It is simultaneously compared with the natural subsidence of soil muddy water in the processing of soil muddy water, (A group is naturally heavy to Fig. 5 soil muddy water
Drop；B group be ZRGO adsorb comparison diagram, each group from left to right be respectively processing 0,10min, 5h, for 24 hours with the effect picture after 7d).
It can be seen that B group graphene oxide in-situ reducing adsorption treatment soil muddy water process, it is (right that 10min can reach purifying water effect
Than natural subsidence process).
Embodiment 3
Actual sewage water sample is simulated, adds five kinds of pollutants (MB, CR, LY, Cd in soil muddy water2+, Pb2+), and be configured to
Two different concentration, 50mg L-1With 250mg L-1Two groups, the graphene oxide being prepared using embodiment 1, according to oxygen
Graphite alkene and pollutant mass ratio are 1:1, and catalyst is ammonium chloride, and reducing agent is zinc powder, the quality of zinc powder and ammonium chloride
Than for 1:3, the mass ratio of graphene oxide and zinc powder is 1:8, the clean-up effect of this method is tested.
5 kinds of pollutants (MB, CR, LY, Cd are added in Fig. 6 soil muddy water2+, Pb2+) treatment effect figure；A group is low concentration
50mg L-1Water sample (A, A1 and A2 be respectively handle 0,10min and for 24 hours after effect picture) and B group be high concentration 250mg L-1
Water sample (B, B1 and B2 be respectively handle 0,10min and for 24 hours after effect picture).
The adsorption efficiency and adsorption capacity ratio of five kinds of pollutants after two kinds of concentration water samples that Fig. 7 is Fig. 6 are handled 10 minutes
Compared with histogram, wherein (a) and (b) is respectively the low concentration group processing adsorption efficiency of each pollutant and absorption after ten minutes in Fig. 6
Capacity histogram；(c) and (d) is respectively that the processing of Fig. 6 middle and high concentration group after ten minutes hold by the adsorption efficiency of each pollutant and absorption
Measure histogram.
Fig. 6 and Fig. 7 show that sewage sample is cleaned as colourless transparent solution, and histogram data is analysis shows that the adsorption process pair
High density pollution object handles its adsorption efficiency and adsorption capacity is above processing low concentration pollutant, and simulation sewage sample processing only needs
10min 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,
Simulation sewage sample processing 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 merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of sewage water treatment method using reducing agent in-situ reducing graphene oxide, which is characterized in that under agitation,
Graphene oxide and reducing agent are added into sewage, is separated by solid-liquid separation, gained liquid phase is that treated sewage；
The reducing agent is used for in-situ reducing graphene oxide；The reducing agent is that normal reduction potential is -2.5V~-0.4V
Metal simple-substance；
Catalyst is additionally added in the sewage, the catalyst is used to be catalyzed the reduction reaction of the reducing agent；The catalysis
Agent is acidic materials；
The reducing agent under the effect of the catalyst, in-situ reducing graphene oxide, and pigment or heavy metal in absorption effluent,
1~it can reach adsorption equilibrium after ten minutes.
2. sewage water treatment method as described in claim 1, which is characterized in that the reducing agent is magnesium powder, aluminium powder, zinc powder and iron
At least one of powder.
3. sewage water treatment method as described in claim 1, which is characterized in that the catalyst is ammonium chloride or phosphoric acid.
4. sewage water treatment method as described in claim 1, which is characterized in that the quality of the reducing agent is the graphite oxide
4 times or more of alkene quality.
5. sewage water treatment method as claimed in claim 3, which is characterized in that the mass ratio of affiliated reducing agent and the catalyst
For 1:1~10.
6. sewage water treatment method as described in claim 1, which is characterized in that the pollutant in the sewage includes pigment or again
Metal.
7. sewage water treatment method as claimed in claim 6, which is characterized in that the matter of the graphene oxide and the pollutant
Amount is than being 0.5~2:1.
8. sewage water treatment method as described in claim 1, which is characterized in that the oxygenation efficiency of the graphene oxide is 100%.
9. sewage water treatment method as claimed in claim 8, which is characterized in that the preparation method of the graphene oxide includes such as
Lower step:
(1) it pre-oxidizes the preparation of graphite: using graphite powder as raw material, sequentially adding the concentrated sulfuric acid, manganese dioxide and phosphorus pentoxide, mix
It closes uniformly and in 60 DEG C~100 DEG C reaction 2h~8h, stratification after cooling down takes lower layer's washing of precipitate to neutrality, is dried to obtain
Pre-oxidize graphite；
(2) it pre-oxidizes the secondary oxidation of graphite: under 0 DEG C of ice bath, the resulting pre-oxidation graphite of step (1) being mixed with the concentrated sulfuric acid
Uniformly, potassium permanganate is added, secondary water and hydrogen peroxide is successively added under agitation after reaction, obtains 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 obtain
Gelatinous graphene oxide.
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| CN110437595B (en) * | 2018-05-03 | 2020-09-18 | 华中科技大学 | Antistatic biodegradable polymer composite material and preparation method thereof |
| 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 |
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