CN110342506A - A kind of graphene oxide continuously prepares purification devices and method - Google Patents
A kind of graphene oxide continuously prepares purification devices and method Download PDFInfo
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- CN110342506A CN110342506A CN201910701163.5A CN201910701163A CN110342506A CN 110342506 A CN110342506 A CN 110342506A CN 201910701163 A CN201910701163 A CN 201910701163A CN 110342506 A CN110342506 A CN 110342506A
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Abstract
Purification devices are continuously prepared the invention discloses a kind of graphene oxide, including reactor, the concentrated sulfuric acid solution storage bottle and water/hydrogen peroxide storage bottle that are connect by delivery pipe with reactor, delivery pipe is equipped with triple valve, the underface of reactor is correspondingly provided with ultrasonic plate with surface, is connected to the first lifting platform of reactor for feeder, agitating paddle and discharge nozzle, discharge nozzle is connect by being equipped with the second delivery pipe of the second peristaltic pump with Filter column, and Filter column is connect by being equipped with the third delivery pipe of third peristaltic pump with graphene oxide storage bottle；The invention also discloses a kind of preparation methods of graphene oxide: strong acid, oxidant separately being fed and graphite oxidation, is removed again and purifying obtains graphene oxide.It is equipped with concentrated sulfuric acid solution storage bottle, feeder, reactor and filter in apparatus of the present invention, realizes the continuous preparation and purification of graphene oxide；What the method for the present invention improved graphene oxide prepares purification efficiency, realizes the recycling of concentrated sulfuric acid solution and continuous utilizes.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of continuous preparation purifying dress of graphene oxide
It sets and method.
Background technique
Graphene is the two dimensional crystal with monoatomic layer thickness being made of carbon atom being stripped out from graphite.Mesh
It is preceding there are many method for preparing graphene, wherein graphene and graphene oxide powder may be implemented in chemistry redox method
Small lot preparation, oxidation-reduction method is the developing direction of preparation of industrialization graphene/graphene oxide.
In oxide-reduction method preparation process, under the action of strong oxidizer, graphite starts to aoxidize graphite, while sulfuric acid
Root is inserted into graphite linings lamella, destroys the conjugation Π key of graphite, and graphite layers are passed through away from 0.9nm~1nm is increased to by 0.34nm
Further thermal expansion is crossed, so that lamella is detached to obtain graphene oxide.Graphene oxide liquid crystal has a series of unique properties,
Its structure includes the phases such as liquid crystal nematic, thin layer, chirality.The liquid crystal of graphene oxide can be used for preparing fiber, self-assembled nanometer
Composite material, energy storage material etc..The optimum preparation condition of graphene oxide is current one of research hotspot.
Tradition prepares the oxidation stripping reaction in graphene oxide method and is not easily controlled at present, leads to graphene oxide ruler
It is very little uneven, and preparation process needs point multistep to carry out, and can not achieve continuous removing and purifying.On the other hand, using a large amount of dense
Sulfuric acid solution realizes graphene oxide removing as reactant, by dilute sulphuric acid heat release, and preparation process needs to extend oxidation stripping
Time from reaction, to avoid vigorous reaction, and there are a large amount of spent acid to pollute environment.Simultaneously using the side such as centrifugation or dialysis
Formula removes the metal ion in graphene oxide, there are problems that low efficiency and wastes water.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of graphene oxide
Continuously prepare purification devices.Be respectively arranged in the device concentrated sulfuric acid solution storage bottle being connect with reactor, offer for into
First lifting platform of glassware and reactor connected pore channel, so that the separated charging of concentrated sulfuric acid solution and potassium permanganate be avoided
The two generates oxidation reaction non-uniform phenomenon after directly largely contacting, and improves the dimensional homogeneity of graphene oxide, while real
The recycling of the continuous preparation and concentrated sulfuric acid solution of graphene oxide is showed, and filter is set after reactor and carries out graphite oxide
The purifying of alkene liquid is continuously to remove metal ion, and purification efficiency is high, and water resource waste is few, realizes the continuous system of graphene oxide
Standby and purifying.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of continuously preparing for graphene oxide is pure
Makeup is set, which is characterized in that the concentrated sulfuric acid solution storage bottle that is connect with reactor by delivery pipe including reactor and respectively and
Water/hydrogen peroxide storage bottle, triple valve is provided in the delivery pipe, and the concentrated sulfuric acid solution storage bottle passes through the first delivery branch pipe and three
Port valve connection, the water/hydrogen peroxide storage bottle are connect by the second delivery branch pipe with triple valve, and the reactor passes through the first conveying
Pipe is connect with triple valve, and the first peristaltic pump is provided in first delivery pipe, is provided with ultrasound immediately below the reactor
Plate is provided with the first lifting platform right above the reactor, is offered respectively on first lifting platform for feeder and anti-
The duct for answering device to be connected to, the duct being connected to for agitating paddle with reactor and the duct being connected to for discharge nozzle with reactor, it is described
Discharge nozzle is connect by the second delivery pipe with the entrance of the Filter column in filter, and it is compacted to be provided with second in second delivery pipe
It is dynamic to pump, the second lifting platform of fixed Filter column is provided with right above the filter, the outlet of the Filter column passes through third
Delivery pipe is connect with graphene oxide storage bottle, is provided with third peristaltic pump in the third delivery pipe.
Graphene oxide preparation process in the prior art is separate operations, is successively added into the reactor equipped with graphene
Enter reactant strong oxidizer concentrated sulfuric acid solution and potassium permanganate, is easy to cause explosion, and due to violent quick between reactant
Effect, causes oxidation reaction non-uniform phenomenon, causes product graphene oxide size uneven.Graphene oxide of the invention
It continuously prepares and is respectively arranged with the concentrated sulfuric acid solution storage bottle connecting with reactor by pipeline in purification devices, offers for charging
First lifting platform of device and reactor connected pore channel, so that concentrated sulfuric acid solution and potassium permanganate are passed through pipeline and feeder respectively
It is added in reactor, realizes the separated charging of strong oxidizer, generate oxidation reaction unevenness after avoiding the two directly contact
Even phenomenon improves the dimensional homogeneity of graphene oxide, realizes the continuous preparation of graphene oxide, while passing through reactor
The first peristaltic pump between concentrated sulfuric acid solution storage bottle in connecting pipe is realized the recycling and continuous utilization of concentrated sulfuric acid solution, is kept away
Exempt to pollute and waste, and by the way that ultrasonic plate is arranged in the underface of reactor, the first peristaltic pump of setting is passed through air and anti-
It answers and agitating paddle progress ultrasound is set in device and is bubbled to assist promoting oxidation reaction, promote the removing of graphene, then in reactor
Setting filter carries out the purifying and storage of graphene oxide liquid afterwards, the continuous purification of graphene oxide is realized, in addition, this hair
Water/hydrogen peroxide storage bottle that bright device setting and reactor are connected by pipeline, using water/hydrogen peroxide to being obtained after aoxidizing
Graphene oxide liquid is removed again, is shortened the time that oxidation reaction is removed, is improved the yield of graphene oxide,
And then it improves the continuous of graphene oxide and prepares purification efficiency.
In addition, the present invention also provides a kind of preparation methods of graphene oxide, which is characterized in that the method includes with
Lower step:
Step 1: concentrated sulfuric acid solution is fitted into concentrated sulfuric acid solution storage bottle, water/hydrogen peroxide is packed into water/hydrogen peroxide storage bottle
In, graphite is fitted into reactor, open and regulating three-way valve connection concentrated sulfuric acid solution storage bottle and reactor and starting it is first compacted
Dynamic pump, fully enters concentrated sulfuric acid solution in reactor, and oxidant potassium permanganate is then added into reactor by feeder
Oxidation reaction is carried out, then opens agitating paddle and ultrasonic plate and continues to start the first peristaltic pump, air is passed through into reactor, is promoted
The progress of oxidation reaction；
Step 2: agitating paddle and ultrasonic plate are closed, by the body of oxidation reaction after to oxidation reaction described in step 1
It is stratification, obtains upper layer reaction acid solution and lower layer's graphene oxide liquid；
Step 3: opening simultaneously regulating three-way valve connection concentrated sulfuric acid solution storage bottle and reactor, and reverse start first is wriggled
The reaction acid solution of upper layer obtained in step 2 is passed sequentially through the first delivery pipe and the first delivery branch pipe enters concentrated sulfuric acid solution by pump
In storage bottle, concentrated sulfuric acid recovered liquid is obtained；
Step 4: opening simultaneously regulating three-way valve connection water/hydrogen peroxide storage bottle and reactor and starting the first peristaltic pump, make
Water/hydrogen peroxide enters in reactor, opens agitating paddle and ultrasonic plate, carries out to lower layer's graphene oxide liquid obtained in step 2
Removing, the graphene oxide liquid removed；
Step 5: the second peristaltic pump of starting, make the graphene oxide liquid of removing obtained in step 4 by discharge nozzle into
Enter in the second delivery pipe, subsequently into purifying is filtered in the Filter column of filter, obtains graphene oxide liquid after purification；
Step 6: starting third peristaltic pump, keeps the graphene oxide liquid obtained in step 5 after purification defeated by third
It send pipe to enter in graphene oxide storage bottle, and then obtains graphene oxide.
Concentrated sulfuric acid solution is first all slowly added into the reactor for filling graphite by the present invention, by feeder by Gao Meng
Sour potassium, which is slowly added into reactor, carries out oxidation reaction, and be aided with ultrasound and ventilation, stirring be bubbled, promote oxidation reaction into
Row, so that graphite layers lamella is sufficiently disengaged to obtain graphene oxide, graphene oxide is deposited on reactant under the effect of gravity
In the solution of system, upper layer reaction acid solution and lower layer's graphene oxide liquid are obtained through stratification, due to the master of upper layer reaction acid solution
Wanting ingredient is the concentrated sulfuric acid, therefore is recycled after upper layer reaction acid pump is gone out, and is added in layer graphene oxide liquid still further below
Enter water/hydrogen peroxide and generate exothermic effects, and be aided with stirring and ultrasound, so that not fully oxidized reaction in lower layer's graphene oxide liquid
Graphite further progress thermally expand removing, obtain graphene oxide, the graphene oxide liquid of removing be finally sent into filter
In be purified by filtration, obtain graphene oxide liquid after purification, and then graphene oxide is prepared.The present invention is by graphite oxide
The preparation and purification of alkene is coupled, and realizes the continuous preparation and purification of graphene oxide, at the same by concentrated sulfuric acid solution and
The difference of potassium permanganate is slowly fed, and is avoided the oxidation reaction non-uniform phenomenon of graphite, is improved the size of graphene oxide
Uniformity, while graphene oxide liquid is removed again, the time that oxidation reaction is removed is shortened, oxidation is improved
The yield of graphene, and then improve the continuous of graphene oxide and prepare purification efficiency, and realize the recycling of concentrated sulfuric acid solution
It is utilized with continuous, avoids pollution and waste.
Above-mentioned method, which is characterized in that graphite described in step 1 is crystalline flake graphite.Using with more excellent layer structure
Crystalline flake graphite as raw material, be more advantageous to sulfate radical and be inserted into the lamella of graphite linings, graphite flake layer is made after thermally expanding
Disengaging obtains graphene oxide.
Above-mentioned method, which is characterized in that the mass concentration of concentrated sulfuric acid solution described in step 1 is 98%, the dense sulphur
Volume, the quality of graphite, the mass ratio of potassium permanganate of acid solution are (12.5~50): 1:(1~3), the unit of volume is
ML, the unit of quality are g；The time of the oxidation reaction is 1h~5h.Above-mentioned raw materials ratio ensure that the suitable of oxidation reaction
Benefit carries out, so that graphite flake layer, which is sufficiently disengaged from, is prepared graphene oxide, in turn avoids reaction material and excessively causes to waste, and protects
Going on smoothly for continuous preparation process is demonstrate,proved, to controlling the time of oxidation reaction in 1h~5h.
Above-mentioned method, which is characterized in that the time of standing described in step 2 is 1h~2h.Due to the mistake of oxidation reaction
It is aided with ultrasound in journey and ventilation, stirring is bubbled, promotes the progress of oxidation reaction, so that graphite is fully converted into graphene oxide and sink
Therefore product will react acid solution by the standing of above-mentioned time with concentrated sulfuric acid upper layer as main component and deposited graphite oxide
Lower layer's graphene oxide liquid of alkene is layered, convenient for the recycling of the concentrated sulfuric acid and the progress of subsequent purification technique.
Compared with the prior art, the present invention has the following advantages:
1, the continuous of graphene oxide of the invention prepares the dense sulphur for being respectively arranged in purification devices and connecting with reactor
Acid solution storage bottle offers the first lifting platform for feeder and reactor connected pore channel, thus by concentrated sulfuric acid solution and Gao Meng
The separated charging of sour potassium generates oxidation reaction non-uniform phenomenon after avoiding the directly a large amount of contacts of the two, improves graphite oxide
The dimensional homogeneity of alkene, while the recycling of the continuous preparation and concentrated sulfuric acid solution of graphene oxide is realized, and after reactor
Filter is set and carries out the purifying of graphene oxide liquid continuously to remove metal ion, purification efficiency is high, and water resource waste is few, real
The continuous preparation and purification of graphene oxide are showed.
2, graphene oxide of the invention continuously prepare in purification devices setting and water that reactor is connected by pipeline/
Hydrogen peroxide storage bottle shortens oxidation reaction and is removed so that the graphene oxide liquid obtained after aoxidizing is removed again
Time, improve the yield of graphene oxide, and then improve graphene oxide continuously prepares purification efficiency.
3, the device of the invention is by being arranged ultrasonic plate in the underface of reactor, the first peristaltic pump of setting be passed through air and
Setting agitating paddle carries out ultrasound and is bubbled to assist promoting oxidation reaction and again release effect in the reactor, further promotes
It is uneven to avoid the graphene oxide degree of oxidation that single stirring or ultrasound are prepared in the prior art for the removings of graphite linings
It is even, and graphene oxide floats on reaction liquid level to be not easy the phenomenon that separating with reaction acid solution, improves graphene oxide
Preparation efficiency.
4, the device of the invention realizes concentrated sulfuric acid solution and separating for potassium permanganate slowly feeds, and it is molten to avoid the concentrated sulfuric acid
Vigorous reaction after liquid and potassium permanganate directly largely contact discharges a large amount of heat and oxygen, hot-spot is caused to lead to reactor
Broken, reaction solution splashes out, and ensure that the safety of graphene oxide preparation.
5, the present invention pass sequentially through strong acid and oxidant separate charging, the oxidation reaction of graphite and again strip operation,
And filter purifying, the preparation and purification of graphene oxide is coupled, realize graphene oxide it is continuous preparation with
Purifying, avoids the oxidation reaction non-uniform phenomenon of graphite, improves the dimensional homogeneity of graphene oxide, improve oxidation stone
Black alkene prepares purification efficiency, realizes the recycling and continuous utilization of concentrated sulfuric acid solution, avoids pollution and waste.
6, lower layer's graphene oxide liquid that the present invention is obtained to oxidation reaction is passed through water/hydrogen peroxide and generates exothermic effects, makes
The graphite further progress for obtaining not fully oxidized reaction in lower layer's graphene oxide liquid thermally expands removing, to be shelled again
From improving the yield of graphene oxide, while reducing the acid concentration in lower layer's graphene oxide liquid, be conducive to subsequent purification
Technique is gone on smoothly；In addition, the hydrogen peroxide being passed through has strong oxidizing property, can make not fully oxidized in lower layer's graphene oxide liquid
The graphite of reaction continues to generate oxidation reaction, further improves the yield of graphene oxide.
7, present invention assisting ultrasonic equal in oxidation reaction and again release effect and stirring, further promote graphene
The removing of piece interlayer improves the preparation rate of graphene oxide, realizes the quick oxidation removing of graphene oxide.
8, the present invention is by controlling the reaction time of oxidation reaction, adjusting oxidation reaction and the again auxiliary in strip operation
Mode, to realize the control of the degree of oxidation of graphite, to realize the classification controllable preparation of the graphene oxide of different-thickness, easily
It is prepared in realization low-cost industrial batch.
Technical solution of the present invention is described in further detail below by drawings and examples.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for continuously preparing purification devices of graphene oxide of the present invention.
Description of symbols:
1-concentrated sulfuric acid solution storage bottle；2-water/hydrogen peroxide storage bottle；The first delivery branch pipe of 3-1-；
The second delivery branch pipe of 3-2-；The first delivery pipe of 3-3-；4-triple valves；
5-the first peristaltic pump；6-reactors；7-feeders；
8-agitating paddles；9-the first lifting platform；10-discharge nozzles；
11-ultrasonic plates；12-the second peristaltic pump；13-the second delivery pipe；
14-the second lifting platform；15-filters；16-Filter columns；
17-third peristaltic pumps；18-third delivery pipes；19-graphene oxide storage bottles.
Specific embodiment
The purification devices that continuously prepare of graphene oxide of the present invention are described in detail by embodiment 1.
Embodiment 1
As shown in Figure 1, the graphene oxide of the present embodiment continuously prepares purification devices and includes reactor 6 and lead to respectively
The concentrated sulfuric acid solution storage bottle 1 and water/hydrogen peroxide storage bottle 2 that delivery pipe is connect with reactor 6 are crossed, is provided with threeway in the delivery pipe
Valve 4, the concentrated sulfuric acid solution storage bottle 1 are connect by the first delivery branch pipe 3-1 with triple valve 4, and the water/hydrogen peroxide storage bottle 2 is logical
It crosses the second delivery branch pipe 3-2 to connect with triple valve 4, the reactor 6 is connect by the first delivery pipe 3-3 with triple valve 4, described
The first peristaltic pump 5 is provided on first delivery pipe 3-3, the underface of the reactor 6 is provided with ultrasonic plate 11, the reactor
6 surface is provided with the first lifting platform 9, offers on first lifting platform 9 and is connected to for feeder 7 with reactor 6 respectively
Duct, the duct being connected to for agitating paddle 8 with reactor 6 and the duct being connected to for discharge nozzle 10 with reactor 6, the discharging
Pipe 10 is connect by the second delivery pipe 13 with the entrance of the Filter column 16 in filter 15, is provided in second delivery pipe 13
Second peristaltic pump 12, the surface of the filter 15 are provided with the second lifting platform 14 of fixed Filter column 16, the Filter column
16 outlet is connect by third delivery pipe 18 with graphene oxide storage bottle 19, and it is compacted to be provided with third in the third delivery pipe 18
Dynamic pump 17.
Graphene oxide of the invention continuously prepares the concentrated sulfuric acid for being respectively arranged in purification devices and connecting with reactor 6
Solution storage bottle 1 offers the first lifting platform 9 for feeder 7 and 6 connected pore channel of reactor, thus by concentrated sulfuric acid solution and height
The separated charging of potassium manganate acutely acts on after avoiding the two directly contact, generates oxidation reaction non-uniform phenomenon, improve oxygen
The dimensional homogeneity of graphite alkene realizes the continuous preparation of graphene oxide, ensure that the safety of graphene oxide preparation,
And can be gone out the upper layer obtained after oxidation reaction reaction acid pump by the first peristaltic pump 5, the recycling of concentrated sulfuric acid solution is realized,
The device of the invention be arranged after reactor 6 filter 15 carry out graphene oxide liquid purifying continuously to remove metal ion,
Purification efficiency is high, and water resource waste is few, to realize the continuous preparation and purification of graphene oxide；The present invention is arranged and reacts
The water that device 6 is connected by pipeline/hydrogen peroxide storage bottle 2 carries out the graphene oxide liquid obtained after aoxidizing using water/hydrogen peroxide
It removes again, shortens the time that oxidation reaction is removed, improve the yield of graphene oxide, and then improve oxidation stone
Black alkene continuously prepares purification efficiency；For the device of the invention by the way that ultrasonic plate is arranged in the underface of reactor, setting first is compacted
Dynamic pump is passed through air and setting agitating paddle carries out ultrasound and is bubbled to assist promoting oxidation reaction and remove again in the reactor
Effect, further promotes the removing of graphite linings, avoids the graphene oxide that ultrasound is prepared in the prior art and floats on
Reaction liquid level improves the preparation efficiency of graphene oxide to be not easy the phenomenon that separating with reaction acid solution.
The preparation method of graphene oxide of the invention is described in detail by 2~embodiment of embodiment 4.
Embodiment 2
The preparation method of the graphene oxide of the present embodiment the following steps are included:
Step 1: the concentrated sulfuric acid solution that 250mL mass concentration is 98% is fitted into concentrated sulfuric acid solution storage bottle 1, water is filled
Enter in water/hydrogen peroxide storage bottle 2,5g crystalline flake graphite is fitted into reactor 6, opens and regulating three-way valve 4 is connected to concentrated sulfuric acid solution
Storage bottle 1 and reactor 6 simultaneously start the first peristaltic pump 5, fully enter 250mL concentrated sulfuric acid solution in reactor 6, then by into
15g oxidant potassium permanganate is added into reactor 6 and carries out oxidation reaction 1h for glassware 7, then opens agitating paddle 8 and ultrasonic plate 11 simultaneously
Continue to start the first peristaltic pump 5, is passed through air into reactor 6, promotes the progress of oxidation reaction；
Step 2: agitating paddle 8 and ultrasonic plate 11 are closed, by oxidation reaction after to oxidation reaction described in step 1
System stratification 1h, obtain upper layer reaction acid solution and lower layer's graphene oxide liquid；
Step 3: opening simultaneously regulating three-way valve 4 is connected to concentrated sulfuric acid solution storage bottle 1 and reactor 6, and reverse start first is compacted
The reaction acid solution of upper layer obtained in step 2 is passed sequentially through the first delivery pipe 3-3 and the first delivery branch pipe 3-1 and entered by dynamic pump 5
In concentrated sulfuric acid solution storage bottle 1, concentrated sulfuric acid recovered liquid is obtained；
It is connected to water/hydrogen peroxide storage bottle 2 and reactor 6 Step 4: opening simultaneously regulating three-way valve 4 and starts the first peristaltic pump 5,
Enter water in reactor 6, opens agitating paddle 8 and ultrasonic plate 11, lower layer's graphene oxide liquid obtained in step 2 is carried out
Removing, the graphene oxide liquid removed；
Step 5: the second peristaltic pump 12 of starting, makes the graphene oxide liquid of removing obtained in step 4 pass through discharge nozzle
10 enter in the second delivery pipe 13, subsequently into purifying is filtered in the Filter column 16 of filter 15, obtain oxygen after purification
Graphite alkene liquid；
Step 6: starting third peristaltic pump 17, makes the graphene oxide liquid obtained in step 5 after purification by third
Delivery pipe 18 enters in graphene oxide storage bottle 19, and then obtains graphene oxide.
Through detecting, the crystalline flake graphite in the present embodiment is completely converted into graphene oxide, and the single layer rate of graphene oxide reaches
To 95%, graphene oxide with a thickness of 0.8nm, and there is good uniformity.
Embodiment 3
The preparation method of the graphene oxide of the present embodiment the following steps are included:
Step 1: the concentrated sulfuric acid solution that 250mL mass concentration is 98% is fitted into concentrated sulfuric acid solution storage bottle 1, by dioxygen
Water is fitted into water/hydrogen peroxide storage bottle 2, and 20g crystalline flake graphite is fitted into reactor 6, opens and regulating three-way valve 4 is connected to the concentrated sulfuric acid
Solution storage bottle 1 and reactor 6 simultaneously start the first peristaltic pump 5, fully enter 250mL concentrated sulfuric acid solution in reactor 6, then lead to
It crosses feeder 7 and 20g oxidant potassium permanganate progress oxidation reaction 5h is added into reactor 6, then open agitating paddle 8 and ultrasonic plate
11 and continue start the first peristaltic pump 5, be passed through air into reactor 6, promote the progress of oxidation reaction；
Step 2: agitating paddle 8 and ultrasonic plate 11 are closed, by oxidation reaction after to oxidation reaction described in step 1
System stratification 2h, obtain upper layer reaction acid solution and lower layer's graphene oxide liquid；
Step 3: opening simultaneously regulating three-way valve 4 is connected to concentrated sulfuric acid solution storage bottle 1 and reactor 6, and reverse start first is compacted
The reaction acid solution of upper layer obtained in step 2 is passed sequentially through the first delivery pipe 3-3 and the first delivery branch pipe 3-1 and entered by dynamic pump 5
In concentrated sulfuric acid solution storage bottle 1, concentrated sulfuric acid recovered liquid is obtained；
It is connected to water/hydrogen peroxide storage bottle 2 and reactor 6 Step 4: opening simultaneously regulating three-way valve 4 and starts the first peristaltic pump 5,
Enter hydrogen peroxide in reactor 6, agitating paddle 8 and ultrasonic plate 11 is opened, to lower layer's graphene oxide liquid obtained in step 2
It is removed, the graphene oxide liquid removed；
Step 5: the second peristaltic pump 12 of starting, makes the graphene oxide liquid of removing obtained in step 4 pass through discharge nozzle
10 enter in the second delivery pipe 13, subsequently into purifying is filtered in the Filter column 16 of filter 15, obtain oxygen after purification
Graphite alkene liquid；
Step 6: starting third peristaltic pump 17, makes the graphene oxide liquid obtained in step 5 after purification by third
Delivery pipe 18 enters in graphene oxide storage bottle 19, and then obtains graphene oxide.
Through detecting, the crystalline flake graphite in the present embodiment is completely converted into graphene oxide, and the single layer rate of graphene oxide reaches
To 90%, graphene oxide with a thickness of 0.9nm, and there is good uniformity.
Embodiment 4
The preparation method of the graphene oxide of the present embodiment the following steps are included:
Step 1: the concentrated sulfuric acid solution that 250mL mass concentration is 98% is fitted into concentrated sulfuric acid solution storage bottle 1, water is filled
Enter in water/hydrogen peroxide storage bottle 2,10g crystalline flake graphite is fitted into reactor 6, opens and regulating three-way valve 4 is connected to concentrated sulfuric acid solution
Storage bottle 1 and reactor 6 simultaneously start the first peristaltic pump 5, fully enter 250mL concentrated sulfuric acid solution in reactor 6, then by into
20g oxidant potassium permanganate is added into reactor 6 and carries out oxidation reaction 3.5h for glassware 7, then opens agitating paddle 8 and ultrasonic plate 11
And continue to start the first peristaltic pump 5, it is passed through air into reactor 6, promotes the progress of oxidation reaction；
Step 2: agitating paddle 8 and ultrasonic plate 11 are closed, by oxidation reaction after to oxidation reaction described in step 1
System stratification 1.5h, obtain upper layer reaction acid solution and lower layer's graphene oxide liquid；
Step 3: opening simultaneously regulating three-way valve 4 is connected to concentrated sulfuric acid solution storage bottle 1 and reactor 6, and reverse start first is compacted
The reaction acid solution of upper layer obtained in step 2 is passed sequentially through the first delivery pipe 3-3 and the first delivery branch pipe 3-1 and entered by dynamic pump 5
In concentrated sulfuric acid solution storage bottle 1, concentrated sulfuric acid recovered liquid is obtained；
It is connected to water/hydrogen peroxide storage bottle 2 and reactor 6 Step 4: opening simultaneously regulating three-way valve 4 and starts the first peristaltic pump 5,
Enter water in reactor 6, opens agitating paddle 8 and ultrasonic plate 11, lower layer's graphene oxide liquid obtained in step 2 is carried out
Removing, the graphene oxide liquid removed；
Step 5: the second peristaltic pump 12 of starting, makes the graphene oxide liquid of removing obtained in step 4 pass through discharge nozzle
10 enter in the second delivery pipe 13, subsequently into purifying is filtered in the Filter column 16 of filter 15, obtain oxygen after purification
Graphite alkene liquid；
Step 6: starting third peristaltic pump 17, makes the graphene oxide liquid obtained in step 5 after purification by third
Delivery pipe 18 enters in graphene oxide storage bottle 19, and then obtains graphene oxide.
Through detecting, the crystalline flake graphite in the present embodiment is completely converted into graphene oxide, and the single layer rate of graphene oxide reaches
To 95%, graphene oxide with a thickness of 0.9nm, and there is good uniformity.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (5)
1. a kind of graphene oxide continuously prepares purification devices, which is characterized in that including reactor (6) and respectively by defeated
The concentrated sulfuric acid solution storage bottle (1) and water for sending pipe to connect with reactor (6)/hydrogen peroxide storage bottle (2) are provided with three in the delivery pipe
Port valve (4), the concentrated sulfuric acid solution storage bottle (1) are connect by the first delivery branch pipe (3-1) with triple valve (4), the water/dioxygen
Water storage bottle (2) is connect by the second delivery branch pipe (3-2) with triple valve (4), and the reactor (6) passes through the first delivery pipe (3-
3) it connect with triple valve (4), is provided with the first peristaltic pump (5) on first delivery pipe (3-3), the reactor (6) is just
Lower section is provided with ultrasonic plate (11), is provided with the first lifting platform (9) right above the reactor (6), first lifting platform
(9) duct being connected to for feeder (7) with reactor (6) is offered on respectively, is connected to for agitating paddle (8) with reactor (6)
Duct and the duct being connected to for discharge nozzle (10) with reactor (6), the discharge nozzle (10) by the second delivery pipe (13) with
The entrance of Filter column (16) in filter (15) connects, and is provided with the second peristaltic pump (12) on second delivery pipe (13),
The second lifting platform (14) of fixed Filter column (16) is provided with right above the filter (15), the Filter column (16) goes out
Mouth is connect by third delivery pipe (18) with graphene oxide storage bottle (19), and it is compacted to be provided with third on the third delivery pipe (18)
Dynamic pump (17).
2. a kind of side for continuously preparing purification devices and preparing graphene oxide using graphene oxide as described in claim 1
Method, which is characterized in that the described method comprises the following steps:
Step 1: concentrated sulfuric acid solution is fitted into concentrated sulfuric acid solution storage bottle (1), water/hydrogen peroxide is packed into water/hydrogen peroxide storage bottle
(2) in, graphite is fitted into reactor (6), opens and regulating three-way valve (4) is connected to concentrated sulfuric acid solution storage bottle (1) and reactor
(6) and start the first peristaltic pump (5), fully enter concentrated sulfuric acid solution in reactor (6), then by feeder (7) to anti-
It answers and oxidant potassium permanganate progress oxidation reaction is added in device (6), then open agitating paddle (8) and ultrasonic plate (11) and continue to start
First peristaltic pump (5) is passed through air in reactor (6), promotes the progress of oxidation reaction；
Step 2: agitating paddle (8) and ultrasonic plate (11) are closed, by oxidation reaction after to oxidation reaction described in step 1
System stratification, obtain upper layer reaction acid solution and lower layer's graphene oxide liquid；
Step 3: opening simultaneously regulating three-way valve (4) connection concentrated sulfuric acid solution storage bottle (1) and reactor (6), and reverse start first
The reaction acid solution of upper layer obtained in step 2 is passed sequentially through the first delivery pipe (3-3) and the first delivery branch pipe by peristaltic pump (5)
(3-1) enters in concentrated sulfuric acid solution storage bottle (1), obtains concentrated sulfuric acid recovered liquid；
Step 4: opening simultaneously regulating three-way valve (4) connection water/hydrogen peroxide storage bottle (2) and reactor (6) and starting the first peristaltic pump
(5), enter water/hydrogen peroxide in reactor (6), agitating paddle (8) and ultrasonic plate (11) are opened, to lower layer obtained in step 2
Graphene oxide liquid is removed, the graphene oxide liquid removed；
Step 5: starting the second peristaltic pump (12), makes the graphene oxide liquid of removing obtained in step 4 pass through discharge nozzle
(10) enter in the second delivery pipe (13), subsequently into purifying is filtered in the Filter column (16) of filter (15), obtain pure
Graphene oxide liquid after change；
Step 6: starting third peristaltic pump (17), keeps the graphene oxide liquid obtained in step 5 after purification defeated by third
It send pipe (18) to enter in graphene oxide storage bottle (19), and then obtains graphene oxide.
3. according to the method described in claim 2, it is characterized in that, graphite described in step 1 is crystalline flake graphite.
4. according to the method described in claim 2, it is characterized in that, the mass concentration of concentrated sulfuric acid solution described in step 1 is
98%, volume, the quality of graphite, the mass ratio of potassium permanganate of the concentrated sulfuric acid solution are (12.5~50): 1:(1~3),
The unit of volume is mL, and the unit of quality is g；The time of the oxidation reaction is 1h~5h.
5. according to the method described in claim 2, it is characterized in that, the time of standing described in step 2 is 1h~2h.
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| CN204999616U (en) * | 2015-07-29 | 2016-01-27 | 上海壹维机电设备有限公司 | Graphite alkene pilot scale production system |
| CN205133157U (en) * | 2015-12-02 | 2016-04-06 | 安徽易能新材料科技有限公司 | Device of integration production oxidation graphite alkene or reduction -oxidation graphite alkene |
| JP2016084266A (en) * | 2014-10-24 | 2016-05-19 | 株式会社TPSTPS Co., Ltd. | Method and apparatus for producing graphene oxide |
| CN109437164A (en) * | 2018-12-07 | 2019-03-08 | 四川聚创石墨烯科技有限公司 | A kind of system by purifying with continuously also preparing graphene originally |
| CN109516456A (en) * | 2018-12-30 | 2019-03-26 | 柳州豪祥特科技有限公司 | A kind of processing method of automobile-used grapheme material |
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| JP2016084266A (en) * | 2014-10-24 | 2016-05-19 | 株式会社TPSTPS Co., Ltd. | Method and apparatus for producing graphene oxide |
| CN204999616U (en) * | 2015-07-29 | 2016-01-27 | 上海壹维机电设备有限公司 | Graphite alkene pilot scale production system |
| CN205133157U (en) * | 2015-12-02 | 2016-04-06 | 安徽易能新材料科技有限公司 | Device of integration production oxidation graphite alkene or reduction -oxidation graphite alkene |
| CN109437164A (en) * | 2018-12-07 | 2019-03-08 | 四川聚创石墨烯科技有限公司 | A kind of system by purifying with continuously also preparing graphene originally |
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