CN105233696B - A kind of method of graphite oxide continuous purification and electrodialysis experimental facilities used - Google Patents
A kind of method of graphite oxide continuous purification and electrodialysis experimental facilities used Download PDFInfo
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Abstract
The present invention relates to a kind of method of graphite oxide continuous purification and electrodialysis experimental facilities used.Electrodialysis plant is divided into four compartments by three kinds of anion-exchange membrane, retention medium, cation-exchange membrane media, and four compartments are respectively cathode chamber, anode chamber, feed liquid room, pure water rooms；Graphite oxide solution circulation to be purified is cleaned and separated using pure water and is further purified until being passed through above-mentioned electrodialysis experimental facilities after its collosol state for being changed into stablizing；Under DC electric field effect, for graphite oxide solution cationic by cation-exchange membrane to cathode chamber, anion first passes through retention medium to pure water rooms, then passes through anion-exchange membrane to anode chamber again；Graphite oxide particle itself is negatively charged, and the Ghandler motion that can equally face south moves, and is trapped within retention medium.This method has the advantages of production efficiency is high, the cycle is short, power consumption is low, water consumption is few, simple to operate.
Description
Technical field
The present invention relates to a kind of method of graphite oxide continuous purification, and in particular to a kind of side of graphite oxide continuous purification
Method and electrodialysis experimental facilities used.
Background technology
Graphite is in strong acid system (such as concentrated sulfuric acid, concentrated nitric acid), through strong oxidizer (such as potassium permanganate, potassium hyperchlorate)
After depth liquid phase oxidation and hydrolysis, graphite oxide is formed.The material is the lamellar compound that a kind of interlamellar spacing is more than former graphite, its
In plane and there are a large amount of oxygen-containing functional groups on edge, show stronger polarity, have specific surface area big and exchange of particles ability
The features such as strong.Graphene using graphite oxide as Material synthesis has the physics such as high conductance, highly thermally conductive, high rigidity and high intensity
And mechanical property, be widely used to electronic device, sensor, lithium ion battery, ultracapacitor, medical carrier, catalyst,
Composite etc..
Preparing the method for graphite oxide mainly has Brodie methods, Staudenmaier methods, Hummer methods and electrochemical oxidation
Method, most widely used at present is Hummer methods.Contain substantial amounts of K in the graphite oxide raw material prepared using Hummer methods+、Na+、Mn2+、H+、NO3 -And SO4 2-, it is necessary to it is purified.Cleaned in water in purge process, because most of metal ion is clear
Lavage, graphite oxide interlayer hydrophilic functional group strengthens with hydrone effect, increases interlamellar spacing, and water absorption and swelling occurs and shows
As solution is changed into collosol state from suspension, and wherein moisture is difficult to separate, and its purifying is also restrained.Aoxidize stone
The purity of black colloidal sol determines its application value.Laboratory is cleaned and centrifuges or filter repeatedly using a large amount of water at present, this method
Water consumption is big, low production efficiency, power consumption height, complex steps.Carried out in addition, also having using conventional electrodialysis plant at purifying
Reason, because graphite oxide particle itself is negatively charged, is easily accumulated on anion-exchange membrane, so as to result in blockage and difficult cleaning
The problem of, it is unfavorable for electrodialytic process and persistently carries out.These methods are not suitable for the operation of graphite oxide continuous purification.
The content of the invention
The present invention is the shortcomings that overcoming in prior art and deficiency, there is provided a kind of production efficiency is high, the cycle is short, power consumption is low,
Water consumption few, the simple to operate method and experimental facilities of realizing graphite oxide continuous purification.
Technical scheme is used by the present invention solves above-mentioned technical problem：
A kind of electrodialysis experimental facilities of graphite oxide continuous purification；Electrodialysis plant is by anion-exchange membrane (A), retention
Three kinds of medium (I), cation-exchange membrane (C) media are divided into four compartments, and four compartments are respectively cathode chamber, anode chamber, feed liquid
Room, pure water rooms；It is anodic-cathodic in electrodialysis plant both sides, there is provided DC electric field；Graphite oxide solution after cleaning is passed through electricity
The feed liquid room of electrodialysis equipment, pure water rooms are passed through pure water, and the anode chamber and the cathode chamber is passed through certain density electrolyte solution.
Described retention medium is filter cloth or polymer matrix, and aperture ratio graphite oxide particle diameter is small.
Described anion-exchange membrane, cation-exchange membrane and retention medium puts in order to be cloudy successively since anode
Amberplex, retention medium, cation-exchange membrane, feed liquid room is cation-exchange membrane and retains the compartment that medium forms, pure
Hydroecium is the compartment of anion-exchange membrane and retention medium composition, and cathode chamber is the compartment where minus plate, and anode chamber is anode
Compartment where plate.
Four compartments are open top end form or four compartments are then closing form.
Four compartments can be open top end form, and feed liquid room need to be stirred；Four compartments are then closing form, are used
Pump carries out circulate operation, and the pressure of feed liquid room is greater than or the pressure equal to pure water rooms, flow 8-15L/h.
A kind of method of graphite oxide continuous purification of the present invention, graphite oxide solution to be purified circulation are clear using pure water
Wash and separate and be further purified until being passed through above-mentioned electrodialysis experimental facilities after its collosol state for being changed into stablizing；In DC electric field
Under effect, for graphite oxide solution cationic by cation-exchange membrane to cathode chamber, anion first passes through retention medium to pure
Hydroecium, then pass through anion-exchange membrane to anode chamber again；Graphite oxide particle itself is negatively charged, and the Ghandler motion that can equally face south moves,
And it is trapped within retention medium.
The solid concentration of described graphite oxide solution to be purified is 5-15g/L.
The ratio between described cleaning graphite oxide pure water dosage and graphite oxide solution volume to be purified are 1:1.
Voltage between two-plate is 5-25V.Electrolyte solution is 10-1000mg/L Na2SO4Solution.
It is described as follows：
There is anodic-cathodic in electrodialysis plant both sides, there is provided DC electric field.Graphite oxide solution after cleaning is passed through the electricity
The feed liquid room of electrodialysis equipment, pure water rooms are passed through pure water, and the anode chamber and the cathode chamber is passed through certain density electrolyte solution.
Described anion and cation exchange membrane is common amberplex, and retention medium is filter cloth or polymer matrix,
Aperture ratio graphite oxide particle diameter is small, and does not allow yielding.
If the graphite oxide amount of required processing is few, four compartments can be open top end form, but need separated in time pair
Feed liquid room is stirred；For mass disposal, four compartments are then closing form, and circulate operation, and feed liquid are carried out using pump
The pressure of room is greater than or the pressure equal to pure water rooms, and flow can be 8-15L/h；
Graphite oxide solution circulation to be purified is cleaned and separated after the collosol state that it is changed into stable using pure water
Above-mentioned electrodialysis experimental facilities is passed through to be further purified.Separate mode is centrifugation after described graphite oxide solution to be purified cleaning
Or filter.The cycle-index separated after described graphite oxide solution to be purified cleaning is 1-3 times.
The method of graphite oxide purifying provided by the invention is based on electrodialytic principle, under DC electric field effect, oxidation
For graphite anions in solution by cation-exchange membrane to cathode chamber, anion first passes through retention medium to pure water rooms, Ran Houzai
Pass through anion-exchange membrane to anode chamber.Graphite oxide particle itself is negatively charged, and the Ghandler motion that can equally face south moves, and is trapped within and cuts
Stay on medium.The problem of so as to prevent graphite oxide to block anion-exchange membrane, it ensure that electrodialytic process is persistently carried out.
This method has the advantages of production efficiency is high, the cycle is short, power consumption is low, water consumption is few, simple to operate.
Brief description of the drawings
The electrodialysis experimental facilities structural principle of Fig. 1 (a) open top end forms
Wherein：1- positive plates, 2- anion-exchange membranes, 3- retentions medium, 4- cation-exchange membranes, 5- minus plates, 6- sun
Pole room, 7- pure water rooms, 8- feed liquids room, 9- cathode chambers
The electrodialysis experimental facilities structural principle of Fig. 1 (b) circulation forms
Wherein：1- positive plates, 2- anion-exchange membranes, 3- retentions medium, 4- cation-exchange membranes, 5- minus plates, 6- sun
Pole room, 7- pure water rooms, 8- feed liquids room, 9- cathode chambers, 10- ammeters, 11- D.C. regulated power supplies, 12- pure water rooms storage tank, 13- sun
Pole room reservoir, 14- cathode chambers reservoir, 15- feed liquids storage tank, 16- cathode chambers circulating pump, 17- feed liquids circulating pump, 18- pure water
Room circulating pump, 19- anode chambers circulating pump, 20- flow control valves
Embodiment
The example of the present invention is elaborated below, the present embodiment is carried out in fact lower premised on technical solution of the present invention
Apply, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
A kind of electrodialysis experimental facilities of graphite oxide continuous purification；Electrodialysis plant is by anion-exchange membrane (A), retention
Three kinds of medium (I), cation-exchange membrane (C) media are divided into four compartments, and four compartments are respectively cathode chamber, anode chamber, feed liquid
Room, pure water rooms；It is anodic-cathodic in electrodialysis plant both sides, there is provided DC electric field；Graphite oxide solution after cleaning is passed through electricity
The feed liquid room of electrodialysis equipment, pure water rooms are passed through pure water, and the anode chamber and the cathode chamber is passed through certain density electrolyte solution.
If the graphite oxide amount of required processing is few, four compartments can be open top end form, but need separated in time pair
Feed liquid room is stirred, as shown in Figure 1a；For mass disposal, four compartments are then closing form, are circulated using pump
Operation, and the pressure of feed liquid room is greater than or the pressure equal to pure water rooms, flow can be 8-15L/h, as shown in Figure 1 b.
A kind of method of graphite oxide continuous purification of the present invention, graphite oxide solution to be purified circulation are clear using pure water
Wash and separate and be further purified until being passed through above-mentioned electrodialysis experimental facilities after its collosol state for being changed into stablizing；In DC electric field
Under effect, for graphite oxide solution cationic by cation-exchange membrane to cathode chamber, anion first passes through retention medium to pure
Hydroecium, then pass through anion-exchange membrane to anode chamber again；Graphite oxide particle itself is negatively charged, and the Ghandler motion that can equally face south moves,
And it is trapped within retention medium.
Embodiment 1：The filter cloth that medium is aperture 5-8um is retained, anion-exchange membrane and cation-exchange membrane are exactly industry
Upper conventional film
Shown in electrodialysis experimental facilities such as Fig. 1 (a), membrane area 100cm2, compartment width 3mm, by three kinds of medium the moon
Four compartment anode chambers (6), the pure water rooms that amberplex (2), retention medium (3), cation-exchange membrane (4) sequentially separate
(7), feed liquid room (8) and cathode chamber (9) composition, and four compartment open top ends, retention medium is using aperture 5-8um, thickness
0.8mm filter cloth, positive plate (1) and minus plate (5) are positioned over equipment both sides, there is provided DC voltage.Diluted and prepared using pure water
Good graphite oxide suspension, is made solid concentration reach 5g/L, takes 30ml, fully cleaned and centrifuged 1 time using 30ml pure water, obtained
Solid phase disperseed again using 30ml pure water, obtained graphite oxide solution is placed in feed liquid room (8), and pure water rooms (7) place pure water,
10mg/L Na is placed in cathode chamber (9) and anode chamber (6)2SO4Solution, both sides loading 5V voltages.Feed liquid room was at interval of 10 minutes hands
Dynamic stirring is once.Two hours of electrodialysis.K+、Na+、Mn2+Ion concentration sum is reduced to 0.39%.
Embodiment 2
Electrodialysis experimental facilities structure the graphite oxide suspension prepared using pure water dilution, makes solid with embodiment 1
Concentration reaches 12.97g/L, takes 30ml, is fully cleaned and centrifuged 2 times using 30ml pure water, and obtained solid phase uses 30ml pure water again
Secondary scattered, obtained graphite oxide solution is placed in feed liquid room (8), and pure water rooms (7) place pure water, cathode chamber (9) and anode chamber (6)
Place 100mg/L Na2SO4Solution, both sides loading 10V voltages.Feed liquid room at interval of 10 minutes hand operated mixings once.Electrodialysis
Two hours.K+、Na+、Mn2+Ion concentration sum is reduced to 0.23%.
Embodiment 3
Electrodialysis experimental facilities structure the graphite oxide suspension prepared using pure water dilution, makes solid with embodiment 1
Concentration reaches 15g/L, takes 30ml, is fully cleaned and centrifuged 3 times using 30ml pure water, obtained solid phase is divided again using 30ml pure water
Dissipate, obtained graphite oxide solution is placed in feed liquid room (8), and pure water rooms (7) place pure water, and cathode chamber (9) and anode chamber (6) are placed
1000mg/L Na2SO4Solution, both sides loading 25V voltages.Feed liquid room at interval of 10 minutes hand operated mixings once.Electrodialysis two
Hour.K+、Na+、Mn2+Ion concentration sum is reduced to 0.21%.
Embodiment 4
Shown in electrodialysis experimental facilities such as Fig. 1 (b), membrane area 100cm2, compartment width 3mm, by three kinds of medium the moon
Four compartment anode chambers (6), the pure water rooms that amberplex (2), retention medium (3), cation-exchange membrane (4) sequentially separate
(7), feed liquid room (8) and cathode chamber (9) composition, and four compartment closings, positive plate (1) and minus plate (5) are positioned over equipment two
Side, DC voltage is provided by D.C. regulated power supply (11), curent change in ammeter (10) electrodialytic process.Oxygen to be purified
Graphite solution is positioned over feed liquid storage tank (15), is circulated by feed liquid circulating pump (17)；Pure water rooms storage tank (12) is placed
100mL pure water, circulated by pure water rooms circulating pump (18)；Cathode chamber reservoir (14) and anode chamber's reservoir (13) are respectively
Place 10mg/L Na2SO4Solution 100mL, circulated by cathode chamber circulating pump (16) and anode chamber's circulating pump (19).Often
Individual compartment can use flow control valve (20) to carry out flow control.The graphite oxide suspension prepared using pure water dilution,
Solid concentration is reached 5mg/mL, take 100mL, fully cleaned and filtered 1 time using 100ml pure water.Obtained filter cake uses 100ml
Pure water disperses again, and obtained graphite oxide solution is positioned over feed liquid storage tank (15), carries out electrodialysis experiment, feed liquid room and pure water
The circular flow of room is controlled in 8L/h or so.In cathode-anode plate both sides using dc source loading 5V voltages.Electrodialysis is two small
When.K+、Na+、Mn2+Ion concentration sum is reduced to 0.64%.
Embodiment 5
Electrodialysis experimental facilities structure the graphite oxide suspension prepared using pure water dilution, makes solid with embodiment 4
Concentration reaches 12.97mg/mL, takes 100mL, is fully cleaned and filtered 2 times using 100ml pure water.Obtained filter cake is pure using 100ml
Water disperses again, and obtained graphite oxide solution is positioned over feed liquid storage tank (15), carries out electrodialysis experiment, feed liquid room and pure water rooms
Circular flow control in 10L/h or so.In cathode-anode plate both sides using dc source loading 10V voltages.Electrodialysis is two small
When.K+、Na+、Mn2+Ion concentration sum is reduced to 0.38%.
Embodiment 6
Electrodialysis experimental facilities structure the graphite oxide suspension prepared using pure water dilution, makes solid with embodiment 4
Concentration reaches 15mg/mL, takes 100mL, is fully cleaned and filtered 3 times using 100ml pure water.Obtained filter cake uses 100ml pure water
Disperse again, obtained graphite oxide solution is positioned over feed liquid storage tank (15), carries out electrodialysis experiment, feed liquid room and pure water rooms
Circular flow is controlled in 15L/h or so.In cathode-anode plate both sides using dc source loading 25V voltages.Two hours of electrodialysis.
K+、Na+、Mn2+Ion concentration sum is reduced to 0.21%.
A kind of method for graphite oxide continuous purification that the present invention is disclosed and proposed and electrodialysis experimental facilities used, this
Art personnel can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although the method for the present invention and
Technology of preparing is described by preferred embodiment, and person skilled can substantially not depart from present invention, essence
Methods and apparatuses described herein is modified or reconfigured in god and scope, to realize final technology of preparing.Especially
It is pointed out that all similar replacements and change it is apparent to those skilled in the art, they all by
It is considered as and is included in spiritual, scope and content of the invention.
Claims (8)
- A kind of 1. electrodialysis experimental facilities of graphite oxide continuous purification；It is characterized in that electrodialysis plant is by anion-exchange membrane (A), three kinds of retention medium (I), cation-exchange membrane (C) media are divided into four compartments, and four compartments are respectively cathode chamber, anode Room, feed liquid room, pure water rooms；It is anodic-cathodic in electrodialysis plant both sides, there is provided DC electric field；Graphite oxide solution after cleaning The feed liquid room of electrodialysis plant is passed through, pure water rooms are passed through pure water, and the anode chamber and the cathode chamber is passed through certain density electrolyte solution；Described Retention medium is filter cloth, and aperture ratio graphite oxide particle diameter is small；Described anion-exchange membrane, cation-exchange membrane and retention Medium put in order for be successively since anode anion-exchange membrane, retention medium, cation-exchange membrane, feed liquid room for sun from The compartment of proton exchange and retention medium composition, the compartment that pure water rooms are anion-exchange membranes with retention medium composition, cathode chamber For the compartment where minus plate, anode chamber is the compartment where positive plate.
- 2. equipment as claimed in claim 1, it is characterized in that four compartments are open top end form or four compartments are enclosed shape Formula.
- 3. equipment as claimed in claim 1, it is characterized in that four compartments are open top end form, feed liquid room need to be stirred Mix；Four compartments are closing form, carry out circulate operation using pump, and the pressure of feed liquid room is greater than or the pressure equal to pure water rooms Power, flow 8-15L/h.
- A kind of 4. method of graphite oxide continuous purification, it is characterised in that graphite oxide solution circulation to be purified uses pure water Clean and separate and be further purified until being passed through any one of the claim 1-3 equipment after its collosol state for being changed into stablizing； Under DC electric field effect, by cation-exchange membrane to cathode chamber, anion first passes through to be cut graphite oxide solution cationic Medium is stayed then to pass through anion-exchange membrane to anode chamber again to pure water rooms；Graphite oxide particle itself is negatively charged, equally can be to Anode moves, and is trapped within retention medium.
- 5. method as claimed in claim 4, it is characterized in that the solid concentration of described graphite oxide solution to be purified is 5- 15g/L。
- 6. method as claimed in claim 4, it is characterized in that described cleaning graphite oxide pure water dosage and oxidation stone to be purified The ratio between black liquor capacity is 1:1.
- 7. method as claimed in claim 4, it is characterized in that the voltage between two-plate is 5-25V.
- 8. method as claimed in claim 4, it is characterized in that electrolyte solution is 10-1000mg/L Na2SO4Solution.
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| WO2013015229A1 (en) * | 2011-07-22 | 2013-01-31 | Semiconductor Energy Laboratory Co., Ltd. | Graphite oxide, graphene oxide or graphene, electric device using the same and method of manufacturing the same, and electrodialysis apparatus |
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