CN110127781A - A kind of modified graphene oxide composite material, preparation method and application - Google Patents
A kind of modified graphene oxide composite material, preparation method and application Download PDFInfo
- Publication number
- CN110127781A CN110127781A CN201910352237.9A CN201910352237A CN110127781A CN 110127781 A CN110127781 A CN 110127781A CN 201910352237 A CN201910352237 A CN 201910352237A CN 110127781 A CN110127781 A CN 110127781A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- modified graphene
- composite material
- modified
- preparation
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of modified graphene oxide composite materials, preparation method and application.The present invention is modified graphene oxide using chitosan, and modified graphene oxide is made；Then modified graphene oxide is added in nanometer calper calcium peroxide preparation solution, modified graphene oxide-nanometer calper calcium peroxide compound is made, finally modified graphene oxide-nanometer calper calcium peroxide compound is loaded on diatomite, a kind of modified graphene oxide composite material is made.This modified graphene oxide composite material large specific surface area, activated adoption bit number of points are more and type is abundant, have efficient adsorption capacity to bio-refractory organic pollutant, metal ion and dyestuff in sewage.Meanwhile the active constituent nanometer calper calcium peroxide in this modified graphene oxide composite material can sustained release go out hydrogen peroxide, in sewage bio-refractory organic matter carry out oxidative degradation, generate the organic pollutant and inorganic matter of bio-degradable.
Description
Technical field
The present invention relates to a kind of sewage treating material, preparation method and application, in particular to a kind of modified graphene oxide
Composite material, preparation method and application.
Background technique
Absorption is to remove a kind of available strategy of dirty water pollutant, is widely used in sewage treatment field.
Graphene oxide is a kind of novel absorption material, maintains the layer structure of graphene, is drawn in each layer of graphene monolithic
A large amount of oxy functional groups are entered, have solved the problems, such as that graphene dissolubility is poor, compound ability is weak.Due to its production cost is low,
Large specific surface area and strong interaction can occur with various anion, cation and the neutral substance in aqueous medium,
Become the research hotspot of technical field of water treatment.It is guiding with target contaminant, modification is oriented to graphene oxide, it can
It assigns graphene oxide new physicochemical property, enhances the adsorption capacity to target contaminant.
Calper calcium peroxide is a kind of high-efficient oxidant of classics, is slightly soluble in water, can slowly decompose in water generate hydrogen peroxide,
Oxygen and calcium hydroxide are widely used in the fields such as agricultural, industry, aquaculture, medicine and environmental protection.With common peroxidating calcium phase
Than nanometer calper calcium peroxide dispersion performance is good, and large specific surface area is more efficient to the oxidative degradation of pollutant.Therefore it can reduce
Calcium oxide usage amount reduces medicament use cost.
Summary of the invention
Goal of the invention: the present invention provides a kind of modified graphene oxide composite materials, preparation method and application.The present invention
Composite material is used as sewage-treating agent, has both absorption and oxidative degradation dual property, forms adsorbing-oxidising degradation compound system,
There is efficient absorption and oxidative degradation ability to bio-refractory organic matter, metal ion and dyestuff in sewage, and can be persistently
It plays a role, wear rate is slow, and it is low to add frequency, solves that traditional wastewater inorganic agent treatment effeciency is low, processing pollutant kind
It is more single, add frequent problem.
Technical solution: a kind of modified graphene oxide composite material of the present invention, the skeleton knot of the composite material
Structure includes at least a kind of component of diatomite, and skeleton structure is formed by viscous viscous stick of glutinous agent；The skeleton structure loads active material,
The active material includes modified graphene oxide and the nanometer calper calcium peroxide for being attached to modified graphene oxide surface；It is described
Modified graphene oxide is chitin modified graphene oxide.
Above-mentioned composite shapes can be cylindric, spherical or irregular particle shape.
Viscous glutinous agent (Bonding agent) for framework material can be natural viscous glutinous agent or the viscous glutinous agent of synthesis, day
Right viscous glutinous agent can be macromolecular polysaccharide class such as starch, carboxymethyl cellulose, protein, dextrin, animal glue, shellac, hide glue
Or rosin, or the mineral binders such as pitch；The viscous glutinous agent of synthesis includes such as polyurethane, polystyrene, and polyacrylate gathers
Vinyl alcohol, ethylene-acetate ethylene copolymer etc..
Preferably water-soluble viscous glutinous agent, most preferably polyvinyl alcohol in the present invention.
Preferably, the mass ratio of the skeleton structure and active material that form composite material is 8~15:1；The active material
In modified graphene oxide and nanometer calper calcium peroxide mass ratio be 1:0.4~0.7；It is aoxidized in the modified graphene oxide
The quality of graphene and chitosan is 1:0.2~0.5.
The composite material is prepared by the following method: being first modified using chitosan to graphene oxide, is made and changes
Property graphene oxide, then modified graphene oxide is placed in nanometer calper calcium peroxide preparation solution, modified graphene oxide-is made and receives
Rice calper calcium peroxide compound, finally loads to modified graphene oxide-nanometer calper calcium peroxide compound on diatomite, is made and changes
Property graphene oxide composite material.
The modified graphene oxide is chitin modified graphene oxide, is changed in the present invention using following methods
Property graphene oxide:
Firstly, graphene oxide is dispersed in aqueous solution, graphene oxide suspension is obtained, it is mixed with chitosan aqueous solution
Close, mixed liquor is placed in autoclave, under the conditions of 160~190 DEG C, is stirred to react, chitosan by with graphite oxide
Carboxyl reaction on alkene obtains then staticly settling the suspension of reaction system by tentatively modified graphene oxide, washing
Wash precipitating；
Then, resulting solid precipitating is added in the aqueous solution containing crosslinking agent, carries out crosslinking fixation, is sufficiently stirred
Reaction system is stood after reaction, and gained washing of precipitate is dry, obtains modified graphene oxide.
Crosslinking agent used can be with are as follows: aldehyde crosslinking agent, such as glutaraldehyde, formaldehyde, glyoxal；Carbodiimides crosslinking
Agent, such as polycarbodiimide；Epoxy crosslinked dose, such as epoxychloropropane.
Preferably crosslinking agent is aldehyde crosslinking agent, most preferably glutaraldehyde, the glutaraldehyde water solution mass concentration of use
It is 0.5~1.5%.
The present invention passes through first high-temperature high-voltage reaction, and the form of rear crosslinking agents crosslinking passes through chitosan and graphene oxide
The chemical bonding that covalent bond carries out, forms modified graphene oxide, modified graphene oxide and graphene oxide of the invention
It is compared with the simple in composition of chitosan, there is more excellent absorption property.
Active material of the present invention is comprising modified graphene oxide and is attached to modified graphene oxide surface
Nanometer calper calcium peroxide, the partial size D10-D90 preferably range of nanometer calper calcium peroxide are 24~174nm.
Nanometer calper calcium peroxide used in the present invention, effect is more preferable, possesses higher oxidative degradation efficiency, compared to common
Calper calcium peroxide, solves that common calper calcium peroxide specific surface area is smaller, to the defect of the oxidative degradation low efficiency of pollutant；And this hair
Bright nanometer calper calcium peroxide is attached to modified graphene oxide surface, solves and directly uses nanometer calper calcium peroxide in the prior art
Because its partial size is small, it is easy to the defect for being washed away, being lost with water flow.
Calper calcium peroxide is attached to modified graphene oxide surface by the following method by the present invention:
Firstly, being dissolved in calcium chloride in the aqueous solution containing cationic surfactant, modified oxidized stone is then added
The mass ratio of black alkene, modified graphene oxide and calcium chloride is 1:2.0~3.5；
Then, after 20~60min of ultrasonic disperse, then 5~20min is mixed slowly, obtains mixed liquor, be then added and account for mixing
Concentrated ammonia liquor (the NH of liquid product 2~6%3Mass percentage be 25~28%), adjust pH value of solution, after mixing, then side
Quickly 4~8 times of heavy hydrogen peroxide of calcium chloride quality (hydrogen peroxide mass percentage is 30%) is added in stirring side, adds subsequent
It is continuous quickly to stir 40~120min, supernatant is removed after standing, gained washing of precipitate is dry, obtain modified graphene oxide-
The active material of nanometer calper calcium peroxide compound composition.
Preferably, cationic surfactant is cetyl trimethylammonium bromide, mass fraction 0.02-0.06%.
Cationic surfactant may make a nanometer calper calcium peroxide is successfully attached to change for generating nano-scale calcium peroxide
Property surface of graphene oxide.
In order to solve water treatment agent in application process, one batch waste water of every processing just adds asking for a water treatment agent
Topic, the present invention are further loaded obtained active material.
Prepare the skeleton structure of supported active material first: the skeleton structure is diatomite composition, and diatomite is added to
In aqueous solution containing viscous glutinous agent, active material is added, continues to stir, is stood after the completion of stirring, gained precipitating is dry to containing
Water rate is 15~40%, is broken into particle；
Then, gained particle is placed in Muffle furnace, 1~2h is calcined under the conditions of 190~220 DEG C, obtains composite material.
By above-mentioned processing, the intensity of the modified graphene oxide composite material ensure that, it in water both can be slow
Dispersion, plays the treatment effect to waste water, but is unlikely to disposably just to be exhausted, and causes the waste of product.
The preparation method of above-mentioned modified graphene oxide composite material, comprising the following steps:
(1) graphene oxide aqueous suspension is mixed with chitosan aqueous solution, is placed in autoclave, at 160~190 DEG C
Under the conditions of react, obtain solid precipitating；
(2) the resulting solid precipitating of step (1) is added in the aqueous solution containing crosslinking agent and is crosslinked, crosslinking finishes
Afterwards, separation solid precipitating, obtains modified graphene oxide；
(3) calcium chloride is dissolved in the aqueous solution containing cationic surfactant, step (2) resulting modification is added
Graphene oxide adds the concentrated ammonia liquor for accounting for mixeding liquid volume 2~6%, and hydrogen peroxide is then added while stirring, and reaction is completed
Afterwards, filtering precipitating obtains the active material being made of modified graphene oxide and nanometer calper calcium peroxide；
(4) diatomite is added in the aqueous solution containing viscous glutinous agent, step (3) resulting active material is added, continues
It stirs, is stood after the completion of stirring, be 15~40% by gained precipitating drying to moisture content, be broken into particle；
(5) by the resulting broken rear particle of step (4), 1~2h is calcined under the conditions of 190~220 DEG C, is obtained modified oxidized
Graphene composite material.
In step (1), the graphene oxide and chitosan and mass ratio be 1:0.2~0.5.
Graphene oxide suspension it is preferred the preparation method comprises the following steps: by graphene oxide in water first ultrasonic disperse 20~
Then 60min mixes slowly 1~3h, obtain graphene oxide suspension.
Chitosan aqueous solution preferred is the preparation method comprises the following steps: add chitosan into the acetic acid solution that mass fraction is 1~5%
In, 20~60min is quickly stirred, chitosan aqueous solution is obtained.
After the mixing of graphene oxide suspension and chitosan aqueous solution, first 20~60min of ultrasonic disperse, then mix slowly
1~3h obtains suspension, suspension is poured into autoclave, sealing is placed in Muffle furnace, under the conditions of 160~190 DEG C
1~2h is reacted, is cooled to room temperature after reaction, obtained precipitating is reaction product；
In step (2), preferred mass concentration is 0.5~1.5% to the crosslinking agent in aqueous solution.
Preferably type of crosslinking agent is one of aldehyde crosslinking agent, Carbodiimides crosslinking agent or epoxides or several
Kind, most preferably, crosslinking agent is glutaraldehyde.
In step (2), when carrying out cross-linking reaction, reaction system is sufficiently stirred, described is sufficiently stirred preferably
Mode is to mix slowly 6~12h, carries out the crosslinking of chitosan and graphene oxide.
In step (2) and step (3), the precipitating obtained after reaction, dry 3 under the conditions of 103~105 DEG C~
5h。
In step (3), the mass ratio of the modified graphene oxide and calcium chloride is 1:2.0~3.5；The calcium chloride with
The mass ratio of hydrogen peroxide is 1:4~8.
In step (3), the surfactant is cationic surface active agent.Preferably six alkyl trimethyl brominations
Ammonium.
In step (3), preferably reaction condition are as follows: prepare the water for the surfactant that mass fraction is 0.02-0.06%
Then solution is added 2.0~3.5 times of modified graphene oxide quality heavy of calcium chloride dissolution, modified graphite oxide is then added
Alkene after 20~60min of ultrasonic disperse, then mixes slowly 5~20min, obtains mixed liquor, be then added account for mixeding liquid volume 2~
6% concentrated ammonia liquor (NH3Content is 25~28%), after mixing, then 4~8 times of calcium chloride quality are added when quickly stirring
The hydrogen peroxide (content of hydrogen peroxide 30%) of weight continues quickly 40~120min of stirring, removes supernatant after standing after adding, will
Gained washing of precipitate is dry, obtains the active material of modified graphene oxide and nanometer calper calcium peroxide compound composition.
In step (4), the mass ratio of diatomite and active material is 8~15:1.
In step (4), it is preferred the preparation method comprises the following steps: will be added to after diatomite drying, grinding mass fraction be 1%~
In 2% poly-vinyl alcohol solution, after quickly stirring 30~60min, active material is added, continues quickly 30~60min of stirring,
After standing, being deposited under the conditions of 50~80 DEG C of obtaining is dried, its moisture content is made to reach 15~40%, obtains modified oxygen
Graphite alkene composite material raw material is crushed resulting modified graphene oxide composite material raw material using crusher, obtains
To composite material granular.
In step (5), the obtained particle based on modified graphene oxide composite material, which is placed in Muffle furnace, to be calcined.
By the processing of step (4) and step (5), the intensity of the modified graphene oxide composite material ensure that,
It both can slowly disperse in water, play the treatment effect to waste water, but be unlikely to disposably just to be exhausted, cause product
Waste.
As preferred mode:
The heretofore described revolving speed that mixes slowly is 150~300rpm, the quick speed of agitator is 301~
500rpm。
The ultrasonic intensity of heretofore described ultrasonic disperse is 4~10kw/m2。
Preferably, the broken partial size of modified graphene oxide raw material is 5~25mm.
The present invention does not use viscous glutinous agent polyvinyl alcohol to carry out viscous, discovery to it when using diatomite as framework material
Composite material of the invention is without legal type.
During the preparation process, the temperature of discovery calcining modified graphene oxide composite material granular is excessively high, such as by the another present invention
250 DEG C, the intensity of composite material can be excessively high, and active material contained by composite material can not be played effectively in sewage disposal process
Effect, but calcination temperature is too low, is such as calcined at 160 DEG C, and the modified graphene oxide composite material of preparation will be made in dirt
It when water process, is disintegrated to be powdered, can not be in granular form.In the present invention, the modified graphene oxide composite material or pass through
Composite material obtained by above-mentioned preparation method is applied in sewage treatment.
In the present invention, application method of the above-mentioned composite material in sewage treatment is by modified graphene oxide composite material
Be layed on the support material layer of water processing reactor bottom, admission space be water processing reactor dischargeable capacity 20~
80%.
Composite material described in the technical program be sustainable effect slow-release medicament, by select diatomite as
The matrix of composite material and select suitable calcination temperature, overcome material meet water easily disperse, easily wash away with water flow, utilization rate it is low
The problem of.The advantage of the technical program, which is once to add, to be used for a long time, easy to operate, and utilization rate is high.
The utility model has the advantages that (1) modified graphene oxide and diatomite all have absorption property, activated adoption site type is rich
Richness, quantity are more, have high efficiency and broad spectrum activity to the absorption of bio-refractory organic matter, metal ion and dyestuff in sewage；(2)
The made water treatment agent wear rate of the present invention is slow, adds that frequency is low, easy to operate, operating cost is low；(3) present invention is made
Water treatment agent chemical property is stablized, and the security risks such as no explosion, burn into poisoning are readily transported and store.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of modified graphene oxide composite material made from the embodiment of the present invention 1；
Fig. 2 is using the independent nanometer calper calcium peroxide grain size distribution obtained of 1 step of the embodiment of the present invention (4)；
Fig. 3 is processing of the modified graphene oxide composite material to rubbish percolation liquid membrane filtered fluid in the embodiment of the present invention 3
Effect picture；
Fig. 4 is modified graphene oxide composite material in the embodiment of the present invention 4 to the treatment effect figure of dyeing waste water.
Specific embodiment
Technical solution of the present invention is further illustrated below with reference to embodiment.
One, raw material sources
Graphene oxide: it is prepared using Hummers method；
The molecular weight of chitosan: 60~120kDa；
The molecular weight of polyvinyl alcohol: 64~114kDa；
Diatomite: SiO2Content >=85%.
Two, sample preparation
Embodiment 1: the preparation of modified graphene oxide composite material:
Step (1): the graphene oxide of 5g is added in the distilled water of 200g, 8kw/m is then used2Ultrasonic intensity
Ultrasonic disperse 30min, then 2h is stirred with 200rpm revolving speed, obtain graphene oxide suspension.The chitosan of 1.5g is added to
In the acetic acid solution that 200g mass fraction is 2%, 40min is stirred with 400rpm revolving speed, obtains chitosan aqueous solution.
Step (2): in graphene oxide suspension resulting with 400rpm revolving speed whipping step (1) by step (1) institute
The chitosan aqueous solution stated is added thereto, and uses 8kw/m2Ultrasonic intensity ultrasonic disperse 30min, then with 200rpm revolving speed stirring
2h obtains suspension.Suspension is poured into autoclave, sealing is placed in Muffle furnace, 1h is reacted under the conditions of 185 DEG C,
It is cooled to room temperature after reaction, spends distilled water for washing of precipitate 3 times, obtain reaction product.
Step (3): step (2) resulting reaction product is added to the water for the glutaraldehyde that 200g mass fraction is 0.8%
In solution, 8h is stirred with 200rpm revolving speed, carries out the crosslinking of chitosan and graphene oxide.It stands, will precipitate after stirring
It is washed with distilled water 3 times, dry 4h, obtains modified graphene oxide under the conditions of 103~105 DEG C.
Step (4): by step (3) 2.5 times of heavy calcium chloride of the modified graphene oxide quality, it is added to 500g mass
In the cationic surface active agent cetyl trimethylammonium bromide aqueous solution that score is 0.02%, stirred with 200rpm revolving speed
It mixes 5min to dissolve to calcium chloride, step (3) resulting modified graphene oxide is added, then with 10kw/m2Ultrasonic intensity
Ultrasonic disperse 30min, then with 200rpm stir 10min, then be added 15mL concentrated ammonia liquor, after mixing again side with 400rpm
Revolving speed stirs side and 5 times of heavy hydrogen peroxide of calcium chloride quality is added, and continues quickly stirring 60min after adding.Supernatant is removed after standing
Precipitating is washed with distilled water 3 times by liquid, and in 103~105 DEG C of dry 3h, it is multiple to obtain modified graphene oxide-nanometer calper calcium peroxide
Close object.
Step (5): by diatomite in 103~105 DEG C of dry 4h, it is obtained modified oxidized that step (4) is weighed after grinding
It is 1% poly-vinyl alcohol solution that graphene-nanometer calper calcium peroxide compound 9 times of weights of quality diatomite, which is added to 500g mass fraction,
In, after stirring 40min with 400rpm revolving speed, it is compound to add modified graphene oxide described in step (4)-nanometer calper calcium peroxide
Object continues to stir 60min with 400rpm revolving speed.It is dry under the conditions of being deposited in 80 DEG C for what is obtained after standing, reach its moisture content
To 25~35%, modified graphene oxide composite material raw material is obtained.
Step (6): being crushed the resulting modified graphene oxide composite material raw material of step (5) using crusher,
Broken size controlling obtains modified graphene oxide composite material granular in 5~15mm.
Step (7): the resulting modified graphene oxide composite material granular of step (6) is placed in Muffle furnace, at 210 DEG C
Under the conditions of calcining 1h to get arrive modified graphene oxide composite material.
Embodiment 2: the preparation of modified graphene oxide composite material
Step (1): the graphene oxide of 5g is added in the distilled water of 200g, 10kw/m is then used2Ultrasonic wave it is strong
Ultrasonic disperse 30min is spent, then 1h is stirred with 200rpm revolving speed, obtains graphene oxide suspension.The chitosan of 2.5g is added
In the acetic acid solution for being 5% to 200g mass fraction, 60min is stirred with 400rpm revolving speed, obtains chitosan aqueous solution.
Step (2): in graphene oxide suspension resulting with 400rpm revolving speed whipping step (1) by step (1) institute
The chitosan aqueous solution stated is added thereto, and uses 10kw/m2Ultrasonic intensity ultrasonic disperse 60min, then stirred with 200rpm revolving speed
3h is mixed, suspension is obtained；Suspension is poured into autoclave, sealing is placed in Muffle furnace, reacts under the conditions of 190 DEG C
1.5h is cooled to room temperature after reaction, with distilled water by washing of precipitate 3 times, obtains reaction product.
Step (3): step (2) resulting reaction product is added to the water for the glutaraldehyde that 200g mass fraction is 1.5%
In solution, 12h is stirred with 200rpm revolving speed, carries out the crosslinking of chitosan and graphene oxide.It stands, will precipitate after stirring
It is washed with distilled water 3 times, dry 4h, obtains modified graphene oxide under the conditions of 103~105 DEG C.
Step (4): by step (3) 3.5 times of heavy calcium chloride of the modified graphene oxide quality, it is added to 500g mass
In the cationic surface active agent cetyl trimethylammonium bromide aqueous solution that score is 0.06%, stirred with 200rpm revolving speed
It mixes 20min to dissolve to calcium chloride, step (3) resulting modified graphene oxide is added, then with 10kw/m2Ultrasonic intensity
Ultrasonic disperse 60min, then with 200rpm stir 20min, then be added 30mL concentrated ammonia liquor, after mixing again side with 400rpm
Revolving speed stirs side and 8 times of heavy hydrogen peroxide of calcium chloride quality is added, and continues quickly stirring 120min after adding.Supernatant is removed after standing
Precipitating is washed with distilled water 3 times by liquid, and in 103~105 DEG C of dry 3h, it is multiple to obtain modified graphene oxide-nanometer calper calcium peroxide
Close object.
Step (5): by diatomite in 103~105 DEG C of dry 4h, it is obtained modified oxidized that step (4) is weighed after grinding
It is that 2% polyvinyl alcohol is molten that graphene-nanometer calper calcium peroxide compound 15 times of weights of quality diatomite, which is added to 500g mass fraction,
In liquid, after stirring 60min with 400rpm revolving speed, it is multiple to add modified graphene oxide described in step (4)-nanometer calper calcium peroxide
Object is closed, continues to stir 60min with 400rpm revolving speed.It is dry under the conditions of being deposited in 80 DEG C for what is obtained after standing, make its moisture content
Reach 25~35%, obtains modified graphene oxide composite material raw material.
Step (6): being crushed the resulting modified graphene oxide composite material raw material of step (5) using crusher,
Broken size controlling obtains modified graphene oxide composite material granular in 5~15mm.
Step (7): the resulting modified graphene oxide composite material granular of step (6) is placed in Muffle furnace, at 210 DEG C
Under the conditions of calcining 1h to get arrive modified graphene oxide composite material.
Embodiment 3: nanometer calper calcium peroxide is prepared using the method for 1 step of embodiment (4), when preparation is added without modified oxidized
Graphene, resulting nanometer calper calcium peroxide use Winner802 photon correlation nanometer laser particle size analyzer determination, and measurement result is shown in figure
2, from figure 2 it can be seen that it is 24~174nm that the particle size range of nanometer calper calcium peroxide of the invention, which is D10-D90, D50 is
77nm, the present invention possess higher oxidative degradation effect by adhering to nanoscale calper calcium peroxide on modified graphene oxide surface
Rate.
Three, application of the modified graphene oxide composite material of the present invention in sewage treatment
Application examples 1:
The application of modified graphene oxide composite material prepared by embodiment 1 as sewage-treating agent, with certain garbage loading embeading
The rubbish percolation liquid membrane concentrate of field is process object, is implemented by following steps:
Step 1: the water processing reactor used is reactor tank, and material is organic glass, high 620mm, and diameter 232mm has
Effect volume be 23.4L, reactor tank away from the 20mm of top at side wall and reactor bottom respectively have a diameter for 12mm aperture.
Step 2: it first is put into the cobble of 15~25mm of partial size in reactor bottom, filling height is 80mm, is added
5.8kg is by modified graphene oxide composite material made from 1 the method for embodiment.
Step 3: rubbish percolation liquid membrane concentrate is flowed into from reactor bottom tapping, from reactor tank upper portion side wall aperture
Place's discharge, inflow velocity 0.7L/min, hydraulic detention time (HRT) are 24min, and the whole service period is 12d.
From the figure 3, it may be seen that rubbish percolation liquid membrane is concentrated in modified graphene oxide composite material within the cycle of operation of 12d
Liquid remains efficient, stable treatment effect.COD,Ca2+、Mg2+Average removal rate be respectively 67.9%, 82.8%
With 75.6%.
Embodiment 4:
The application of modified graphene oxide composite material prepared by embodiment 1 as sewage-treating agent, with certain printing and dyeing mill
Dyeing waste water is process object, is implemented by following steps:
Step 1: with 1 step 1 of application examples.
Step 2: with 1 step 2 of application examples.
Step 3: dyeing waste water is flowed into from reactor bottom aperture, is discharged from reactor tank upper portion side wall aperture, inflow velocity
For 0.93L/min, HRT 18min, the whole service period is 12d.
As shown in Figure 4, modified graphene oxide composite material equally has good treatment effect to dyeing waste water, COD,
Chroma removal rate has respectively reached 75.0% and 79.8%.
Claims (9)
1. a kind of modified graphene oxide composite material, which is characterized in that the skeleton structure of the composite material includes at least silicon
A kind of component of diatomaceous earth, skeleton structure are formed by viscous viscous stick of glutinous agent；The skeleton structure loads active material, the active material
Comprising modified graphene oxide and it is attached to the nanometer calper calcium peroxide on modified graphene oxide surface；The modified graphite oxide
Alkene is chitin modified graphene oxide.
2. modified graphene oxide composite material according to claim 1, which is characterized in that the skeleton structure and activity
The mass ratio of material is 8~15:1；The mass ratio of modified graphene oxide and nanometer calper calcium peroxide in the active material is
1:0.4~0.7；The quality of graphene oxide and chitosan is 1:0.2~0.5 in the modified graphene oxide.
3. a kind of preparation method of modified graphene oxide composite material, which comprises the following steps:
(1) graphene oxide aqueous suspension is mixed with chitosan aqueous solution, is placed in autoclave, in 160~190 DEG C of conditions
Lower reaction obtains solid precipitating；
(2) the resulting solid precipitating of step (1) is added in the aqueous solution containing crosslinking agent and is crosslinked, after crosslinking,
Solid precipitating is separated, modified graphene oxide is obtained；
(3) calcium chloride is dissolved in the aqueous solution containing cationic surfactant, it is resulting modified oxidized that step (2) is added
Graphene adds the concentrated ammonia liquor for accounting for mixeding liquid volume 2~6%, and hydrogen peroxide, after the reaction was completed, mistake are then added while stirring
Filter precipitating, obtains the active material being made of modified graphene oxide and nanometer calper calcium peroxide；
(4) diatomite is added in the aqueous solution containing viscous glutinous agent, step (3) resulting active material is added, continues to stir,
It is stood after the completion of stirring, is 15~40% by gained precipitating drying to moisture content, is broken into particle；
(5) by the resulting broken rear particle of step (4), 1~2h is calcined under the conditions of 190~220 DEG C, obtains modified graphite oxide
Alkene composite material.
4. the preparation method of modified graphene oxide composite material according to claim 3, which is characterized in that step (1)
In, the graphene oxide and chitosan and mass ratio be 1:0.2~0.5.
5. the preparation method of modified graphene oxide composite material according to claim 3, which is characterized in that step (2)
In, the crosslinking agent is one or more of aldehyde crosslinking agent, Carbodiimides crosslinking agent or epoxides.
6. the preparation method of modified graphene oxide composite material according to claim 3, which is characterized in that step (3)
In, the mass ratio of the modified graphene oxide and calcium chloride is 1:2.0~3.5；The mass ratio of the calcium chloride and hydrogen peroxide
For 1:4~8.
7. the preparation method of modified graphene oxide composite material according to claim 3, which is characterized in that step (4)
In, the mass ratio of diatomite and active material is 8~15:1.
8. compound obtained by composite material as claimed in claim 1 or 2 or any preparation method of claim 3-7
Material is applied in sewage treatment.
9. application according to claim 8, which is characterized in that application method is to spread modified graphene oxide composite material
On the support material layer of sewage-treating reactor bottom, admission space be sewage-treating reactor dischargeable capacity 20~
80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910352237.9A CN110127781B (en) | 2019-04-29 | 2019-04-29 | Modified graphene oxide composite material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910352237.9A CN110127781B (en) | 2019-04-29 | 2019-04-29 | Modified graphene oxide composite material, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110127781A true CN110127781A (en) | 2019-08-16 |
| CN110127781B CN110127781B (en) | 2022-05-10 |
Family
ID=67575385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910352237.9A Active CN110127781B (en) | 2019-04-29 | 2019-04-29 | Modified graphene oxide composite material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110127781B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112316893A (en) * | 2020-10-22 | 2021-02-05 | 华东理工大学 | Preparation method and application of bentonite composite material for adsorbing and degrading site odor substances |
| CN113896453A (en) * | 2021-10-27 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Modified graphene composite material and preparation method thereof, cement reinforcing agent and application thereof |
| CN114835477A (en) * | 2021-02-25 | 2022-08-02 | 李婷 | Multifunctional water purification ceramic material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601155A (en) * | 2013-11-18 | 2014-02-26 | 同济大学 | Method for preparing nano calcium peroxide by chemical modification |
| CN109019825A (en) * | 2018-10-09 | 2018-12-18 | 宁波沸柴机器人科技有限公司 | A kind of efficient treating agent for papermaking wastewater and its preparation method and application |
| US10759681B2 (en) * | 2018-06-28 | 2020-09-01 | Board Of Trustees Of The University Of Arkansas | Water purification compositions and the method of producing the same |
-
2019
- 2019-04-29 CN CN201910352237.9A patent/CN110127781B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601155A (en) * | 2013-11-18 | 2014-02-26 | 同济大学 | Method for preparing nano calcium peroxide by chemical modification |
| US10759681B2 (en) * | 2018-06-28 | 2020-09-01 | Board Of Trustees Of The University Of Arkansas | Water purification compositions and the method of producing the same |
| CN109019825A (en) * | 2018-10-09 | 2018-12-18 | 宁波沸柴机器人科技有限公司 | A kind of efficient treating agent for papermaking wastewater and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 中国核学会: "《中国核科学技术发展进展报告第5卷第8册》", 30 April 2018, 中国原子能出版社 * |
| 朱双: "粉煤灰/壳聚糖/氧化石墨烯复合材料的制备", 《工程科技Ⅰ辑(月刊)》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112316893A (en) * | 2020-10-22 | 2021-02-05 | 华东理工大学 | Preparation method and application of bentonite composite material for adsorbing and degrading site odor substances |
| CN112316893B (en) * | 2020-10-22 | 2023-07-07 | 华东理工大学 | Preparation method and application of bentonite composite material for adsorbing and degrading site peculiar smell substances |
| CN114835477A (en) * | 2021-02-25 | 2022-08-02 | 李婷 | Multifunctional water purification ceramic material |
| CN114835477B (en) * | 2021-02-25 | 2023-10-31 | 潮州市新成陶瓷有限公司 | Multifunctional water purification ceramic material |
| CN113896453A (en) * | 2021-10-27 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Modified graphene composite material and preparation method thereof, cement reinforcing agent and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110127781B (en) | 2022-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110127781A (en) | A kind of modified graphene oxide composite material, preparation method and application | |
| CN104031651B (en) | Passivation improver for heavy metal pollution farmland and using method thereof | |
| CN105214629A (en) | A kind of biomass-based nano lanthanum oxide dephosphorization compound adsorbent and preparation method thereof | |
| CN105131960A (en) | Preparation method and application of lead-polluted soil restoration material | |
| CN107082894A (en) | A kind of double-network hydrogel adsorbent and preparation method thereof and it is used as the application of heavy metal absorbent | |
| CN105399963B (en) | A kind of mechanical activation method for preparing solid phase of lignocellulosic ester group oxidation catalyst | |
| CN108480380B (en) | In-situ and ex-situ saline soil remediation method for ultrasonic deep leaching coupled nano rock composite modifier | |
| CN105148854A (en) | Preparation method of mesoporous silica solidified laccase printing and dyeing wastewater decolorizer | |
| CN111233304B (en) | Wall breaking agent for sludge, hydrophobic skeleton, preparation method and sludge reduction method | |
| CN104761117B (en) | A kind of sludge viscosity reducing process | |
| CN106268673B (en) | A kind of preparation method of amino modified chitosan composite adsorbing material | |
| CN109759032A (en) | A kind of regulatable preparation method for carrying lanthanum magnetic hydrogel composite adsorbing material of charge | |
| CN109876780A (en) | A kind of dephosphorization adsorbent and preparation method thereof | |
| CN105969371A (en) | Soil repairing agent by taking garden waste as main raw material | |
| CN111040769B (en) | Soil restoration improving agent and soil restoration improving method | |
| CN107281998A (en) | Modified magnetic alumina adsorbant and its preparation method and application | |
| CN111996008B (en) | Method for immobilizing humic acid on surface of shell natural material | |
| CN105329972A (en) | Straw composite material preparation method | |
| CN105969377A (en) | Clayey soil conditioner | |
| CN115055157A (en) | Preparation and desorption method of zirconium modified zeolite-bentonite active particle dephosphorization filter material | |
| CN101469144A (en) | Composite nano titanium dioxide and preparation thereof | |
| CN105032917B (en) | Chromium slag leachate contamination soil emergence treating method | |
| CN105967936A (en) | Molybdenum-tailings-improved soil mineral remediation agent | |
| CN105944671B (en) | A kind of preparation method, product and the application of bamboo absorbent charcoal and the compound photocatalysis water-purifying material of graft modification corncob | |
| CN109482137A (en) | A kind of production method of fast filter atlapulgite |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |