CN108298721A - A kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling - Google Patents
A kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling Download PDFInfo
- Publication number
- CN108298721A CN108298721A CN201810111593.7A CN201810111593A CN108298721A CN 108298721 A CN108298721 A CN 108298721A CN 201810111593 A CN201810111593 A CN 201810111593A CN 108298721 A CN108298721 A CN 108298721A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- graphite oxide
- colloidal sol
- graphite
- oxide colloidal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
-
- 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
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to graphite oxide technical field more particularly to a kind of methods of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, include at least following steps：Step 1, the flocculation of graphite oxide；Step 2, the reduction plastic of graphite oxide；Step 3 neutralizes, adsorption treatment.The a large amount of graphite oxides wherein dissolved are fully recycled while the present invention is directed to carry out high-efficiency cleaning processing to colloidal sol waste liquid, wide adaptation range, scalability are strong, it is widely portable to any concentration and the acid/base waste liquid of pH, and can realize industrial grade oxygen graphite waste water low cost recycling.
Description
Technical field
The invention belongs to graphite oxide technical field more particularly to a kind of graphite oxide colloidal sol waste liquid cleaning treatment and recycling
The method utilized.
Background technology
In the past decade, graphene is considered as being based on physics, chemistry, material science and engineering and field of biology
Promising commercial application material.With scientific technological advance, demand of the market to new material drastically increases, world wide
Interior " graphene thermal " has had reached quite high level.Therefore, many companies have begun to be dedicated to ton (flaky material/
Three-dimensional material) or hundreds thousand of square metres of (thin-film material) grade commercial Applications grapheme material production.
There are mainly three types of the magnanimity preparation methods of graphene, including the direct liquid phase stripping method of graphite, chemical vapour deposition technique
And oxidation and subsequent peeling or/and the reduction method of graphite.The direct liquid phase stripping method of graphite is at low cost, but there are do not have largely
The graphite of stripping must be driven off so that this process yield is low；Graphene quality that chemical vapour deposition technique obtains and yield compared with
The direct liquid phase stripping means of graphite is high, but its cost is also higher；The oxidation of graphite and subsequent peeling or/and reduction method
(Hummers methods) is current most common graphene magnanimity preparation method, due to this method high income, at low cost, expansible
Property it is good, become very competitive method, every year use this method production grapheme material reached ten-million-ton scale.But
It is that this method will produce a large amount of graphite oxide cleaning waste liquids, and the oxygen containing considerable amount during preparing graphene
Graphite urgently recycles.In addition, graphite oxide also be studied be considered a kind of oxygen-containing functional group be prevalent in single layer,
sp3Hydbridized carbon atoms layer is prevalent in sp2The multifunctional material of hydridization carbon network, thus it is used for two-dimentional material by a large number of researchers
Material is modified and the research of composite material, is widely studied and uses.
It flourishes with grapheme material field is commercialized, no matter graphite oxide was prepared as graphene technical grade
The intermediate product of journey or a kind of basic material being concerned, the cleaning treatment of waste liquid and recycling have become a weight
Big challenge.A kind of colloidal sol waste liquid of the graphite oxide waste liquid as stabilization is needed using the common physical treatment method for centrifuging, filtering
It wants quite high centrifugal speed, large-scale centrifugation apparatus or expends the very long suction filtration time, equipment and time cost are high, and aoxidize
Recycling graphite rate is low.
In conclusion the present invention is intended to provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling,
The a large amount of graphite oxides dissolved in waste liquid can fully be recycled and colloidal sol waste liquid is changed into clear waste water with after an action of the bowels
Continuous processing and reuse.This method wide adaptation range, scalability are strong, and the acid/base for being widely portable to any concentration and pH is useless
Liquid, and can realize industrial grade oxygen graphite waste water low cost recycling, therefore, this method will have considerable in practical applications
Economic benefit and social benefit.
Invention content
It is an object of the invention to：In view of the deficiencies of the prior art, it provides at a kind of graphite oxide colloidal sol waste liquid cleaning
Reason and the method recycled can fully recycle a large amount of graphite oxides dissolved in waste liquid and turn colloidal sol waste liquid
Become clear waste water so as to subsequent processing and reuse.This method wide adaptation range, scalability are strong, are widely portable to arbitrary
The acid/base waste liquid of concentration and pH, and can realize industrial grade oxygen graphite waste water low cost recycling, therefore, this method will be
There is considerable economic benefit and social benefit in practical application.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling includes at least following steps：
Step 1, flocculation, flocculant is added in graphite oxide colloidal sol waste liquid, and flocculation is stood after stirring and obtains concentration oxidation
Graphite sol waste liquid and supernatant liquor；
Step 2 restores plastic, the concentration graphite oxide colloidal sol waste liquid that step 1 obtains is stirred evenly, and is then added also
Former agent is sufficiently stirred to obtain mixed dispersion liquid, and it is anti-that the mixed dispersion liquid is put into normal pressure isothermal reaction or progress hydro-thermal in container
It answers, or step 1 is obtained into concentration graphite oxide colloidal sol waste liquid and is added in container and carries out hydro-thermal reaction, obtain reduction-oxidation
Graphite hydrogel and clear aqueous solution；
Step 3: the clear aqueous solution that the supernatant liquor of step 1 and step 2 are obtained passes through neutralization, adsorption treatment simultaneously
Reuse.
Graphite oxide not only rapidly can be separated from the water out, leave during flocculating and restoring plastic
Clear aqueous solution can also take away the metal ion in waste water by larger specific surface area, play adsorption cleaning waste water
Effect.
As the improved technical solution of the present invention, the reduction-oxidation graphite hydrogel obtained in step 2 is steamed by capillary
Hair carries out moisture removal, obtains three-dimensional dense porous graphite oxide macroscopic body.Wherein, described that moisture is carried out by capillary evaporation
The method of removing is that room temperature is dried or heating, drying, temperature are 20 DEG C -90 DEG C, duration 6h-72h.In drying course, profit
With the capillary evaporation of water, the contraction to material is realized.20 DEG C -90 DEG C may be implemented block and preferably shrink, while avoiding higher
Block caused by rapid desufflation crushes under temperature condition；The abundant drying to material may be implemented in the drying time of 6h-72h.Institute
The specific surface area 100-600m for the dense porous reduction-oxidation graphite macroscopic body of three-dimensional stated2/ g, Kong Rongwei 0.1-0.5cm3/ g, block
Volume density is 1-1.6g/cm3。
The present invention use mild condition reduction treatment, can fully recycle dissolved in graphite oxide waste liquid it is a large amount of
Graphite oxide, and can realize the cleaning treatment of colloidal sol waste liquid, and it is widely used in any concentration and the acid/base waste liquid of pH, it can
It realizes the inexpensive recycling treatment of industrial grade oxygen graphite waste water, there is considerable economic benefit and social benefit.
That is, using the method for the present invention, in any concentration with the graphite oxide colloidal sol waste liquid of arbitrary pH value
Effectively concentration can be achieved and prepare to form three-dimensional reduction-oxidation graphite hydrogel, and this method is to graphite oxide colloidal sol waste liquid
Volume is without any requirement.This method scalability is strong, can realize the graphite oxide waste water low cost recycling treatment of technical grade.
As a kind of improvement of graphite oxide colloidal sol waste liquid cleaning treatment of the present invention and the method for recycling, in step 1
The flocculant include aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride, aluminium polychloride, polyaluminium sulfate, poly-ferric chloride,
In bodied ferric sulfate, polyacrylamide, polyvinyl alcohol, Aspergillus sojae, biological flocculant NOC-1 and biological flocculant PF101
It is at least one.
As a kind of improvement of graphite oxide colloidal sol waste liquid cleaning treatment of the present invention and the method for recycling, in step 1
The graphite oxide colloidal sol waste liquid comes from graphite oxide eccentric cleaning waste liquid, graphite oxide modified-reaction waste liquid and graphite oxide
At least one of recombination reaction waste liquid.
As a kind of improvement of graphite oxide colloidal sol waste liquid cleaning treatment of the present invention and the method for recycling, step 2 institute
The reducing agent stated includes hydrazine hydrate, ethylenediamine, urea, thiocarbamide, hydrogen peroxide, ammonium hydroxide, sodium borohydride, potassium borohydride, vulcanized sodium, Asia
Sodium sulphate, frerrous chloride, ferrous sulfate, hydroxylamine, ascorbic acid, sodium ascorbate, hydroiodic acid, ethanedioic acid, hydroquinone, aniline,
At least one of pyrroles, pyrogaelol, sodium citrate and sodium hydrogensulfite.
As a kind of improvement of graphite oxide colloidal sol waste liquid cleaning treatment of the present invention and the method for recycling, step 2
It concentrates in graphite oxide colloidal sol waste liquid, the mass ratio of graphite oxide and reducing agent is (1-30)：1.
As a kind of improvement of graphite oxide colloidal sol waste liquid cleaning treatment of the present invention and the method for recycling, step 2
In, the temperature of normal pressure isothermal reaction is 40-120 DEG C, duration of the reaction 2-36h；The temperature of the hydro-thermal reaction is
120-250 DEG C, duration of the reaction 3-48h.
As a kind of improvement of graphite oxide colloidal sol waste liquid cleaning treatment of the present invention and the method for recycling, in step 3
The method of the neutralization is acid, alkali waste water neutralisation, dispensing neutralisation or filtering neutralisation.
As a kind of improvement of graphite oxide colloidal sol waste liquid cleaning treatment of the present invention and the method for recycling, adsorption treatment
The adsorbent used is at least one of activated carbon, humic acid, sepiolite, polysaccharide resins, montmorillonite, for further removing
The impurity metal ion dissolved in waste water.Further, it is also possible to which the dense porous graphene oxide macroscopic body of the three-dimensional is used for institute
The adsorption treatment in step 3 is stated, it is possible thereby to further realize oneself of graphite oxide waste liquid using graphite oxide waste liquid itself
It is clean.
Compared with prior art, the invention has the advantages that：
First, this method mild condition is easy to operate, greatly reduces liquid waste processing by the method for flocculation concentration first
Amount, then by being added after a small amount of reducing agent down to liquid waste processing is completed at 40 DEG C, both realized the clear of graphite oxide colloidal sol waste liquid
Clean processing, and fully recycled a large amount of graphite oxides wherein dissolved and obtained three-dimensional dense porous graphite oxide material, it is real
The inexpensive recycling treatment of graphite oxide colloidal sol waste liquid is showed, there is considerable economic benefit and social benefit.
Second, the three-dimensional reduction-oxidation graphite hydrogel prepared by this method can be with the oxidation stone in 100% Recycling of waste liquid
Ink, and by the abundant oxygen-containing functional group in its surface and specific surface area, at the same band leak water in a large amount of metal impurities ions, obtain
Clear aqueous solution.The three-dimensional dense porous graphite oxide material of gained be it is a kind of have abundant pore structure, large specific surface area,
The formed blocks material of greater density.The present invention simple and quick can not only obtain limpid waste water, also using graphite oxide and
The larger specific surface area adsorbing metal ions of three-dimensional dense porous graphite oxide material, itself play the work of adsorption cleaning waste water
With.
Third, the present invention can waste liquid caused by the industrial applications towards grapheme material, it is wide adaptation range, expansible
Property is strong, can be widely used in any concentration and the acid/base graphite oxide colloidal sol waste liquid of pH, and liquid waste processing amount can reach
Technical grade can become the important ring in complete grapheme material industrial chain.
Description of the drawings
Fig. 1 is graphite oxide colloidal sol waste liquid flocculation figure in embodiment 1.
Fig. 2 is that concentration graphite oxide colloidal sol waste liquid reduction reaction obtains reduction-oxidation graphite hydrogel and clear in embodiment 1
Clear water solution figure.
Fig. 3 is the inductance coupling that colloidal sol waste liquid isolates manganese ion in gained clear aqueous solution after graphite oxide in embodiment 1
Close plasma emission spectroscopy (ICP-OES) test curve.
Specific implementation mode
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto.
Embodiment 1
Present embodiments provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, including following step
Suddenly：
Step 1: (coming from graphite oxide eccentric cleaning to the 5L graphite oxide colloidal sols waste liquid that pH is 3 a concentration of 0.6mg/mL
Waste liquid) in 15mL polyacrylamide solutions are added dropwise, 6h is stood after stirring and flocculates to obtain concentration graphite oxide colloidal sol waste liquid and upper layer
Clear liquid (as shown in Figure 1)；
It is stirred evenly Step 2: concentration graphite oxide colloidal sol waste liquid is poured into glass beaker, 3g sodium ascorbates is added,
Stirring 15min makes it be sufficiently mixed, and obtains mixed dispersion liquid；By in the addition glass container of mixed dispersion liquid, recycled in 50 DEG C
Normal pressure isothermal reaction 6h in water-bath obtains reduction-oxidation graphite hydrogel and clear aqueous solution (as shown in Figure 2)；
Further, the hydrogel that step 2 obtains is placed 72h in ventilation at room temperature to dry, moisture in dry process
It is removed by capillary evaporation, obtains three-dimensional dense porous reduction-oxidation graphite macroscopic body；
Step 3: 20mg is added in the supernatant liquor that step 1 obtains and the clear aqueous solution that step 2 obtains while stirring
Sodium hydroxide is neutralized to pH as the metal ion in 7, addition 50mg block absorbent charcoals absorption water.
Practice have shown that：For reduction-oxidation graphite hydrogel at more regular cylindric, what is obtained after flocculation and plastic is pending useless
Clarification of water is colourless.The specific surface area of the obtained dense porous reduction-oxidation graphite macroscopic body of three-dimensional is 207m2/g.Before processing, oxygen
The content of manganese ion is 5.9mg/mL in graphite colloidal sol waste liquid, and manganese ion content is in step 1 treated supernatant liquor
2.1mg/L, the content of manganese ion is 1.6mg/mL (as shown in Figure 3), step 3 in step 2 treated clear aqueous solution
Manganese ion content in treated water is 0.8mg/mL, reaches discharging standards.
Embodiment 2
Present embodiments provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, including following step
Suddenly：
Step 1: (useless from graphite oxide modified-reaction to the 5L graphite oxide colloidal sols waste liquid that pH is 5 a concentration of 1mg/mL
Liquid) in 15mL poly-vinyl alcohol solutions are added dropwise, 8h is stood after stirring and flocculates to obtain concentration graphite oxide colloidal sol waste liquid and supernatant liquor；
It is stirred evenly Step 2: concentration graphite oxide colloidal sol waste liquid is poured into glass beaker, 4g sodium citrates is added, stir
Mixing 30min makes it be sufficiently mixed, and obtains mixed dispersion liquid；The glass beaker of mixed dispersion liquid will be filled, in 80 DEG C of circulator baths
Middle normal pressure isothermal reaction 4h, obtains reduction-oxidation graphite hydrogel and clear aqueous solution；
Further, reduction-oxidation graphite hydrogel is carried out in deionized water adequately impregnating 30h, at room temperature in logical
It places 60h at wind to dry, moisture is removed by capillary evaporation in dry process, obtains three-dimensional dense porous oxygen reduction fossil
Black macroscopic body；
Step 3: ammonium hydroxide is added in the supernatant liquor that step 1 obtains and the clear aqueous solution that step 2 obtains while stirring
PH is neutralized to as the metal ion in 7, addition 80mg bulk montmorillonites absorption water.
Practice have shown that：For reduction-oxidation graphite hydrogel at more regular cylindric, what is obtained after flocculation and plastic is pending useless
Clarification of water is colourless.The specific surface area of the obtained dense porous reduction-oxidation graphite macroscopic body of three-dimensional is 220m2/g.Before processing, oxygen
The content of manganese ion is 8mg/mL in graphite colloidal sol waste liquid, and manganese ion content is in step 1 treated supernatant liquor
2.3mg/L, the content of manganese ion is 1.4mg/mL in step 2 treated clear aqueous solution, in step 3 treated water
Manganese ion content be 0.7mg/mL, reach discharging standards.
Embodiment 3
Present embodiments provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, including following step
Suddenly：
Step 1: (coming from graphite oxide recombination reaction to the 5L graphite oxide colloidal sols waste liquid that pH is 4 a concentration of 1.6mg/mL
Waste liquid) in 25mL polymeric ferrous sulphate solutions are added dropwise, 3h is stood after stirring and flocculates to obtain concentration graphite oxide colloidal sol waste liquid and upper layer
Clear liquid；
It is stirred evenly Step 2: concentration graphite oxide colloidal sol waste liquid is poured into glass beaker, 1.6g ethylenediamines is added, stir
Mixing 50min makes it be sufficiently mixed, and obtains mixed dispersion liquid, and the mixed dispersion liquid is poured into reaction kettle, anti-in 180 DEG C of hydro-thermals
5h is answered, reduction-oxidation graphite hydrogel and clear aqueous solution are obtained；
Further, reduction-oxidation graphite hydrogel is carried out in deionized water adequately impregnating 20h, then heating is dried
Dry, temperature is 70 DEG C, duration 10h, and moisture is removed by capillary evaporation in drying course, is obtained three-dimensional fine and close more
Hole reduction-oxidation graphite macroscopic body；
Step 3: the supernatant liquor that step 1 obtains and the clear aqueous solution that step 2 obtains are made by filtering neutralisation
Its pH is 7, the dense porous reduction-oxidation graphite macroscopic body of the addition three-dimensional adsorbs the metal ion in water.
Practice have shown that：For reduction-oxidation graphite hydrogel at more regular cylindric, what is obtained after flocculation and plastic is pending useless
Clarification of water is colourless.The specific surface area of the obtained dense porous reduction-oxidation graphite macroscopic body of three-dimensional is 311m2/g.Before processing, oxygen
The content of manganese ion is 13.6mg/mL in graphite colloidal sol waste liquid, and manganese ion content is in step 1 treated supernatant liquor
2.5mg/L, the content of manganese ion is 1.23mg/mL in step 2 treated clear aqueous solution, step 3 treated water
In manganese ion content be 0.73mg/mL, reach discharging standards.
Embodiment 4
Present embodiments provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, including following step
Suddenly：
Step 1: (useless from graphite oxide recombination reaction to the 5L graphite oxide colloidal sols waste liquid that pH is 2 a concentration of 2mg/mL
Liquid) in 5mL biological flocculant NOC-1 are added dropwise, stand that 4h flocculates to obtain concentration graphite oxide colloidal sol waste liquid and upper layer is clear after stirring
Liquid；
It is stirred evenly Step 2: concentration graphite oxide colloidal sol waste liquid is poured into glass beaker, 10g urea, stirring is added
35min makes it be sufficiently mixed, and obtains mixed dispersion liquid, and the mixed dispersion liquid is poured into reaction kettle, in 140 DEG C of hydro-thermal reactions
7h obtains reduction-oxidation graphite hydrogel and clear aqueous solution；
Further, reduction-oxidation graphite hydrogel is carried out in deionized water adequately impregnating 15h, then heating is dried
Dry, temperature is 60 DEG C, duration 16h, and moisture is removed by capillary evaporation in drying course, is obtained three-dimensional fine and close more
Hole reduction-oxidation graphite macroscopic body；
Step 3: the supernatant liquor that step 1 obtains and the clear aqueous solution that step 2 obtains are made by neutralisation of offeing medicine
Its pH is 7, addition 35mg bulk polysaccharide resins adsorb the metal ion in water.
Practice have shown that：For reduction-oxidation graphite hydrogel at more regular cylindric, what is obtained after flocculation and plastic is pending useless
Clarification of water is colourless.The specific surface area of the obtained dense porous reduction-oxidation graphite macroscopic body of three-dimensional is 186m2/g.Before processing, oxygen
The content of manganese ion is 15.2mg/mL in graphite colloidal sol waste liquid, and manganese ion content is in step 1 treated supernatant liquor
2.9mg/L, the content of manganese ion is 1.4mg/mL in step 2 treated clear aqueous solution, in step 3 treated water
Manganese ion content be 0.86mg/mL, reach discharging standards.
Embodiment 5
Present embodiments provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, including following step
Suddenly：
Step 1: (useless from graphite oxide modified-reaction to the 5L graphite oxide colloidal sols waste liquid that pH is 6 a concentration of 4mg/mL
Liquid) in 4mL aluminum sulfate is added dropwise, 5h is stood after stirring and flocculates to obtain concentration graphite oxide colloidal sol waste liquid and supernatant liquor；
It is stirred evenly Step 2: concentration graphite oxide colloidal sol waste liquid is poured into glass beaker, 1g hydrazine hydrates, stirring is added
25min makes it be sufficiently mixed, and obtains mixed dispersion liquid, and the mixed dispersion liquid is poured into reaction kettle, in 160 DEG C of hydro-thermal reactions
13h obtains reduction-oxidation graphite hydrogel and clear aqueous solution；
Further, reduction-oxidation graphite hydrogel is carried out in deionized water adequately impregnating 22h, then heating is dried
Dry, temperature is 75 DEG C, duration 13h, and moisture is removed by capillary evaporation in drying course, is obtained three-dimensional fine and close more
Hole reduction-oxidation graphite macroscopic body；
Step 3: ammonium hydroxide is added in the supernatant liquor that step 1 obtains and the clear aqueous solution that step 2 obtains while stirring
PH is neutralized to as the metal ion in 7, addition 45mg bulk humic acids absorption water.
Practice have shown that：For reduction-oxidation graphite hydrogel at more regular cylindric, what is obtained after flocculation and plastic is pending useless
Clarification of water is colourless.The specific surface area of the obtained dense porous reduction-oxidation graphite macroscopic body of three-dimensional is 253m2/g.Before processing, oxygen
The content of manganese ion is 20.3mg/mL in graphite colloidal sol waste liquid, and manganese ion content is in step 1 treated supernatant liquor
3.1mg/L, the content of manganese ion is 1.5mg/mL in step 2 treated clear aqueous solution, in step 3 treated water
Manganese ion content be 0.9mg/mL, reach discharging standards.
Embodiment 6
Present embodiments provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, include at least with
Lower step：
Step 1: (coming from graphite oxide recombination reaction to the 5L graphite oxide colloidal sols waste liquid that pH is 4.5 a concentration of 6mg/mL
Waste liquid) in 7mL aluminium polychlorides are added dropwise, 10h is stood after stirring and flocculates to obtain concentration graphite oxide colloidal sol waste liquid and supernatant liquor；
It is stirred evenly Step 2: concentration graphite oxide colloidal sol waste liquid is poured into glass beaker, 13g sodium sulfites is added,
Stirring 35min makes it be sufficiently mixed, and obtains mixed dispersion liquid, the mixed dispersion liquid is poured into reaction kettle, in 170 DEG C of hydro-thermals
11h is reacted, reduction-oxidation graphite hydrogel and clear aqueous solution are obtained；
Further, reduction-oxidation graphite hydrogel is carried out in deionized water adequately impregnating 15h, then heating is dried
Dry, temperature is 65 DEG C, duration 8h, and moisture is removed by capillary evaporation in drying course, is obtained three-dimensional fine and close more
Hole reduction-oxidation graphite macroscopic body；
Step 3: hydrogen-oxygen is added in the supernatant liquor that step 1 obtains and the clear aqueous solution that step 2 obtains while stirring
Change sodium and is neutralized to pH as the metal ion in 7, addition 25mg block absorbent charcoals absorption water；
Practice have shown that：For reduction-oxidation graphite hydrogel at more regular cylindric, what is obtained after flocculation and plastic is pending useless
Clarification of water is colourless.The specific surface area of the obtained dense porous reduction-oxidation graphite macroscopic body of three-dimensional is 151m2/g.Before processing, oxygen
The content of manganese ion is 23.9mg/mL in graphite colloidal sol waste liquid, and manganese ion content is in step 1 treated supernatant liquor
3.5mg/L, the content of manganese ion is 1.2mg/mL in step 2 treated clear aqueous solution, in step 3 treated water
Manganese ion content be 0.83mg/mL, reach discharging standards.
Embodiment 7
Present embodiments provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, include at least with
Lower step：
Step 1: (compound anti-from graphite oxide to the 5L graphite oxide colloidal sols waste liquid that pH is 2.5 a concentration of 5.5mg/mL
Answer waste liquid) in 7mL biological flocculant NOC-1 are added dropwise, 12h is stood after stirring and flocculates to obtain concentration graphite oxide colloidal sol waste liquid and upper
Layer clear liquid；
Step 2: concentration graphite oxide colloidal sol waste liquid is added to the container, in 190 DEG C of hydro-thermal reaction 10h, oxygen reduction is obtained
Graphite hydrogel and clear aqueous solution；
Further, reduction-oxidation graphite hydrogel is carried out in deionized water adequately impregnating 12h, then heating is dried
Dry, temperature is 75 DEG C, duration 7.5h, and moisture is removed by capillary evaporation in drying course, obtains three-dimensional densification
Porous reduction-oxidation graphite macroscopic body；
Step 3: hydrogen-oxygen is added in the supernatant liquor that step 1 obtains and the clear aqueous solution that step 2 obtains while stirring
Change sodium and is neutralized to pH as the metal ion in 7, addition 25mg block absorbent charcoals absorption water；
Practice have shown that：For reduction-oxidation graphite hydrogel at more regular cylindric, what is obtained after flocculation and plastic is pending useless
Clarification of water is colourless.The specific surface area of the obtained dense porous reduction-oxidation graphite macroscopic body of three-dimensional is 155m2/g.Before processing, oxygen
The content of manganese ion is 25.7mg/mL in graphite colloidal sol waste liquid, and manganese ion content is in step 1 treated supernatant liquor
2.5mg/L, the content of manganese ion is 1.1mg/mL in step 2 treated clear aqueous solution, in step 3 treated water
Manganese ion content be 0.81mg/mL, reach discharging standards.
Embodiment 8
Present embodiments provide a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, include at least with
Lower step：
Step 1: (being modified to the 5L graphite oxide colloidal sols waste liquid that pH is 3.5 a concentration of 8.5mg/mL from graphite oxide anti-
Answer waste liquid) in 7mL Aspergillus sojaes are added dropwise, 7h is stood after stirring and flocculates to obtain concentration graphite oxide colloidal sol waste liquid and supernatant liquor；
Step 2: concentration graphite oxide colloidal sol waste liquid is added to the container, in 185 DEG C of hydro-thermal reaction 15h, oxygen reduction is obtained
Graphite hydrogel and clear aqueous solution；
Further, reduction-oxidation graphite hydrogel is carried out in deionized water adequately impregnating 8h, then heating is dried
Dry, temperature is 85 DEG C, duration 8.5h, and moisture is removed by capillary evaporation in drying course, obtains three-dimensional densification
Porous reduction-oxidation graphite macroscopic body；
Step 3: hydrogen-oxygen is added in the supernatant liquor that step 1 obtains and the clear aqueous solution that step 2 obtains while stirring
Change sodium and is neutralized to pH as the metal ion in 7, addition 25mg block absorbent charcoals absorption water；
Practice have shown that：For reduction-oxidation graphite hydrogel at more regular cylindric, what is obtained after flocculation and plastic is pending useless
Clarification of water is colourless.The specific surface area of the obtained dense porous reduction-oxidation graphite macroscopic body of three-dimensional is 159m2/g.Before processing, oxygen
The content of manganese ion is 25.0mg/mL in graphite colloidal sol waste liquid, and manganese ion content is in step 1 treated supernatant liquor
1.3mg/L, the content of manganese ion is 1.0mg/mL in step 2 treated clear aqueous solution, in step 3 treated water
Manganese ion content be 0.51mg/mL, reach discharging standards.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in specific implementation modes disclosed and described above, to the present invention's
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification
Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling, includes the following steps：
Step 1, flocculation, flocculant is added in graphite oxide colloidal sol waste liquid, and flocculation is stood after stirring and obtains concentration graphite oxide
Colloidal sol waste liquid and supernatant liquor；
Step 2 restores plastic, the concentration graphite oxide colloidal sol waste liquid that step 1 obtains is stirred evenly, reducing agent is then added
It is sufficiently stirred to obtain mixed dispersion liquid, above-mentioned mixed dispersion liquid is put into normal pressure isothermal reaction in container or carries out hydro-thermal reaction,
Or the concentration graphite oxide colloidal sol waste liquid that step 1 obtains is added to the container carry out hydro-thermal reaction, to obtain reduction-oxidation
Graphite hydrogel and clear aqueous solution；
Step 3: the clear aqueous solution that the supernatant liquor of step 1 and step 2 are obtained is by neutralizing, adsorption treatment simultaneously reuse.
2. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 1, it is characterised in that：
The reduction-oxidation graphite hydrogel that step 2 is obtained carries out moisture removal by capillary evaporation, obtains three-dimensional dense porous oxidation
Graphite macroscopic body.
3. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 2, it is characterised in that：
The method for carrying out moisture removal by capillary evaporation is that room temperature is dried or heating, drying, temperature are 20 DEG C -90 DEG C, is held
The continuous time is 6 h-72 h.
4. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 2 or 3, feature exist
In：By the dense porous graphene oxide macroscopic body of the three-dimensional for the adsorption treatment in the step 3.
5. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 1, it is characterised in that：
Flocculant described in step 1 includes aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride, aluminium polychloride, polyaluminium sulfate, gathers
Close iron chloride, bodied ferric sulfate, polyacrylamide, polyvinyl alcohol, Aspergillus sojae, biological flocculant NOC-1 and biological flocculant
At least one of PF101.
6. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 1, it is characterised in that：
Graphite oxide colloidal sol waste liquid described in step 1 from graphite oxide eccentric cleaning waste liquid, graphite oxide modified-reaction waste liquid and
At least one of graphite oxide recombination reaction waste liquid.
7. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 1, it is characterised in that：
Reducing agent described in step 2 include hydrazine hydrate, ethylenediamine, urea, thiocarbamide, hydrogen peroxide, ammonium hydroxide, sodium borohydride, potassium borohydride,
Vulcanized sodium, sodium sulfite, frerrous chloride, ferrous sulfate, hydroxylamine, ascorbic acid, sodium ascorbate, hydroiodic acid, ethanedioic acid, to benzene two
At least one of phenol, aniline, pyrroles, pyrogaelol, sodium citrate and sodium hydrogensulfite.
8. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 1, it is characterised in that：
In step 2, the mass ratio of graphite oxide and reducing agent is（1-30）：1.
9. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 1, it is characterised in that：
In step 2, the temperature of normal pressure isothermal reaction is 40-120 DEG C, duration of the reaction 2-36h；The temperature of hydro-thermal reaction is
120-250 DEG C, duration of the reaction 3-48h.
10. the method for graphite oxide colloidal sol waste liquid cleaning treatment and recycling according to claim 1, feature exist
In：The adsorbent that adsorption treatment uses is at least one of activated carbon, humic acid, sepiolite, polysaccharide resins, montmorillonite, is used
The impurity metal ion dissolved in further removing waste water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810111593.7A CN108298721A (en) | 2018-02-05 | 2018-02-05 | A kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810111593.7A CN108298721A (en) | 2018-02-05 | 2018-02-05 | A kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108298721A true CN108298721A (en) | 2018-07-20 |
Family
ID=62864174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810111593.7A Pending CN108298721A (en) | 2018-02-05 | 2018-02-05 | A kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108298721A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793143A (en) * | 2018-08-15 | 2018-11-13 | 南通百川新材料有限公司 | Industrial production method of graphene |
| CN109319875A (en) * | 2018-11-22 | 2019-02-12 | 合肥景观园林工程有限责任公司 | A kind of underground water Compound Heavy Metals renovation agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482613A (en) * | 2013-09-03 | 2014-01-01 | 中国科学院山西煤炭化学研究所 | High-efficiency separation and purification method of graphite oxide |
| CN105836742A (en) * | 2016-06-17 | 2016-08-10 | 西北师范大学 | Method for preparing three-dimensional network-like structure graphene |
-
2018
- 2018-02-05 CN CN201810111593.7A patent/CN108298721A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482613A (en) * | 2013-09-03 | 2014-01-01 | 中国科学院山西煤炭化学研究所 | High-efficiency separation and purification method of graphite oxide |
| CN105836742A (en) * | 2016-06-17 | 2016-08-10 | 西北师范大学 | Method for preparing three-dimensional network-like structure graphene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793143A (en) * | 2018-08-15 | 2018-11-13 | 南通百川新材料有限公司 | Industrial production method of graphene |
| CN109319875A (en) * | 2018-11-22 | 2019-02-12 | 合肥景观园林工程有限责任公司 | A kind of underground water Compound Heavy Metals renovation agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104826582B (en) | A kind of preparation method of graphene meso-porous titanium dioxide silica aerogel | |
| CN102974307B (en) | Functionalized graphene adsorbent and preparation method and application thereof | |
| CN105032375B (en) | Preparation method of magnetic graphite-based heavy metal adsorbing material | |
| CN102000573B (en) | Modified activated carbon and application thereof | |
| CN105214607B (en) | Preparation method, redox graphene and its application of redox graphene | |
| CN101805037B (en) | Method for removing humic acid pollutants in water by magnetic chitosan particle | |
| CN107213881A (en) | A kind of Preparation method and use of activated carbon base Inorganic whisker section bar material | |
| CN105664963A (en) | Ozone catalyst for water treatment and preparation method thereof | |
| CN109225138B (en) | Modified activated carbon for efficiently adsorbing AOCs in PTA wastewater and preparation method thereof | |
| CN105289562B (en) | Heavy metal wastewater thereby recoverying and utilizing method | |
| CN105251462A (en) | Garbage penetrating fluid efficient wastewater treating agent based on modified fly ash and preparation method | |
| CN106693923A (en) | Gel for recovering phosphorus from water and preparation method and application thereof | |
| CN109289772B (en) | Carbon nano tube/hydrotalcite material for removing nitrate nitrogen in water and preparation method thereof | |
| CN106745651B (en) | Method for treating organic wastewater by using ferric oxychloride to catalytically activate peroxydisulfate | |
| CN104071785B (en) | A kind of method preparing the Graphene with three-dimensional macro vesicular structure | |
| CN109569536A (en) | A kind of modified alta-mud and its preparation process | |
| CN108298721A (en) | A kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling | |
| CN109437462A (en) | A kind of processing method of pyridine waste water | |
| CN107552052B (en) | Treatment method of refractory organic wastewater | |
| CN106902758A (en) | A kind of preparation and application of the Graphene adsorbent of aerobic particle mud N doping | |
| Zolfaghari et al. | Surface modification of ordered nanoporous carbons CMK-3 via a chemical oxidation approach and its application in removal of lead pollution from water | |
| CN104148004A (en) | Magnetic fluorine ion adsorbent and preparation method thereof | |
| CN105417800B (en) | A kind of method that environmental protection removes nitrate nitrogen in waste water | |
| CN107159119A (en) | The preparation method of the nano-fibre supported montmorillonite defluorination material of porous activated carbon | |
| CN110606649A (en) | Sludge conditioning and dewatering method and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180720 |
|
| RJ01 | Rejection of invention patent application after publication |