CN110342506B - Continuous preparation and purification device and method for graphene oxide - Google Patents
Continuous preparation and purification device and method for graphene oxide Download PDFInfo
- Publication number
- CN110342506B CN110342506B CN201910701163.5A CN201910701163A CN110342506B CN 110342506 B CN110342506 B CN 110342506B CN 201910701163 A CN201910701163 A CN 201910701163A CN 110342506 B CN110342506 B CN 110342506B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- reactor
- sulfuric acid
- concentrated sulfuric
- acid solution
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a continuous preparation and purification device of graphene oxide, which comprises a reactor, a concentrated sulfuric acid solution storage bottle and a water/hydrogen peroxide solution storage bottle which are connected with the reactor through a conveying pipe, wherein a three-way valve is arranged on the conveying pipe, ultrasonic plates, a feeder, a stirring paddle and a first lifting platform of a discharging pipe which are communicated with the reactor are correspondingly arranged right below and right above the reactor, the discharging pipe is connected with a filter column through a second conveying pipe provided with a second peristaltic pump, and the filter column is connected with the graphene oxide storage bottle through a third conveying pipe provided with a third peristaltic pump; the invention also discloses a preparation method of the graphene oxide, which comprises the following steps: and (3) separately feeding the strong acid and the oxidant, oxidizing the strong acid and the oxidant with graphite, and stripping and purifying to obtain the graphene oxide. The device is provided with a concentrated sulfuric acid solution storage bottle, a feeder, a reactor and a filter, so that the continuous preparation and purification of the graphene oxide are realized; the method improves the preparation and purification efficiency of the graphene oxide, and realizes the recovery and continuous utilization of concentrated sulfuric acid solution.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a continuous preparation and purification device and method for graphene oxide.
Background
Graphene is a two-dimensional crystal composed of carbon atoms exfoliated from graphite with a monoatomic layer thickness. At present, there are various methods for preparing graphene, wherein a chemical oxidation-reduction method can realize small-batch preparation of graphene and graphene oxide powder, and the oxidation-reduction method is a development direction for industrially preparing graphene/graphene oxide.
In the preparation process of the redox method, under the action of a strong oxidant, graphite begins to be oxidized, meanwhile, sulfate radicals are inserted into graphite layer sheets to destroy conjugated pi bonds of the graphite, the spacing between the graphite layers is increased from 0.34nm to 0.9 nm-1 nm, and the sheets are separated through further thermal expansion to obtain the graphene oxide. Graphene oxide liquid crystals have a series of unique properties, and the structures of the graphene oxide liquid crystals comprise liquid crystal nematic, thin layers, chirality and the like. The liquid crystal of the graphene oxide can be used for preparing fibers, self-assembled nano composite materials, energy storage materials and the like. Optimization of the preparation process of graphene oxide is one of the current research hotspots.
At present, the oxidation stripping reaction in the traditional method for preparing the graphene oxide is not easy to control, so that the size of the graphene oxide is not uniform, the preparation process needs to be carried out in multiple steps, and continuous stripping and purification cannot be realized. On the other hand, a large amount of concentrated sulfuric acid solution is used as a reactant, graphene oxide stripping is realized by diluting sulfuric acid to release heat, the time of an oxidation stripping reaction needs to be prolonged in the preparation process so as to avoid a violent reaction, and a large amount of waste acid is present to pollute the environment. Meanwhile, metal ions in the graphene oxide are removed by adopting modes such as centrifugation or dialysis, and the problems of low efficiency and water waste exist.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a continuous preparation and purification apparatus for graphene oxide, aiming at the above-mentioned deficiencies of the prior art. Be provided with the concentrated sulfuric acid solution storage bottle of being connected with the reactor in the device respectively, set up the first elevating platform that supplies feeder and reactor intercommunication pore, thereby with the separately feeding of concentrated sulfuric acid solution and potassium permanganate, the inhomogeneous phenomenon of oxidation reaction has been produced after having avoided both direct large amount of contacts, the size uniformity of graphite oxide has been improved, the continuous preparation of graphite oxide and the recovery of concentrated sulfuric acid solution have been realized simultaneously, and set up the filter behind the reactor and carry out the purification of graphite oxide liquid in order to get rid of metal ion in succession, purification efficiency is high, the water waste is few, the continuous preparation and the purification of graphite oxide have been realized.
In order to solve the technical problems, the invention adopts the technical scheme that: a continuous preparation and purification device of graphene oxide is characterized by comprising a reactor, a concentrated sulfuric acid solution storage bottle and a water/hydrogen peroxide storage bottle which are respectively connected with the reactor through conveying pipes, wherein a three-way valve is arranged on each conveying pipe, the concentrated sulfuric acid solution storage bottle is connected with the three-way valve through a first conveying branch pipe, the water/hydrogen peroxide storage bottle is connected with the three-way valve through a second conveying branch pipe, the reactor is connected with the three-way valve through a first conveying pipe, a first peristaltic pump is arranged on each first conveying pipe, an ultrasonic plate is arranged under the reactor, a first lifting table is arranged right above the reactor, a pore passage for communicating a feeder and the reactor is respectively arranged on each first lifting table, a pore passage for communicating a stirring paddle and the reactor and a pore passage for communicating a discharging pipe and the reactor are respectively arranged on each first lifting table, the discharging pipe is connected with an inlet of a filter column in the filter through a second conveying pipe, the second conveying pipe is provided with a second peristaltic pump, a second lifting platform for fixing the filter column is arranged right above the filter, an outlet of the filter column is connected with the graphene oxide storage bottle through a third conveying pipe, and the third conveying pipe is provided with a third peristaltic pump.
The graphene oxide preparation process in the prior art is a step-by-step operation, reactant strong oxidant concentrated sulfuric acid solution and potassium permanganate are sequentially added into a reactor filled with graphene, so that explosion is easily caused, and due to the violent rapid action among reactants, the phenomenon of nonuniform oxidation reaction is caused, and the size of the product graphene oxide is nonuniform. The continuous preparation and purification device of the graphene oxide is respectively provided with a concentrated sulfuric acid solution storage bottle connected with a reactor through a pipeline and a first lifting platform provided with a pore passage for communicating a feeder with the reactor, so that the concentrated sulfuric acid solution and potassium permanganate are respectively added into the reactor through the pipeline and the feeder, the separate feeding of a strong oxidant is realized, the phenomenon of nonuniform oxidation reaction after the concentrated sulfuric acid solution and the potassium permanganate are directly contacted is avoided, the size uniformity of the graphene oxide is improved, the continuous preparation of the graphene oxide is realized, meanwhile, the recovery and the continuous utilization of the concentrated sulfuric acid solution are realized through a first peristaltic pump on the pipeline connected between the reactor and the concentrated sulfuric acid solution storage bottle, the pollution and the waste are avoided, an ultrasonic board is arranged under the reactor, the first peristaltic pump is arranged to introduce air, and a stirring paddle is arranged in the reactor to carry out ultrasonic and bubbling to assist in promoting the oxidation reaction, the device provided by the invention is provided with a water/hydrogen peroxide storage bottle connected with the reactor through a pipeline, and the oxidized graphene liquid obtained after oxidation is peeled again by adopting water/hydrogen peroxide, so that the peeling time of the oxidation reaction is shortened, the yield of the oxidized graphene is improved, and the continuous preparation and purification efficiency of the oxidized graphene is further improved.
In addition, the invention also provides a preparation method of the graphene oxide, which is characterized by comprising the following steps:
step one, filling a concentrated sulfuric acid solution into a concentrated sulfuric acid solution storage bottle, filling water/hydrogen peroxide into the water/hydrogen peroxide storage bottle, filling graphite into a reactor, opening and adjusting a three-way valve to communicate the concentrated sulfuric acid solution storage bottle with the reactor and starting a first peristaltic pump, so that the concentrated sulfuric acid solution completely enters the reactor, then adding an oxidant potassium permanganate into the reactor through a feeder to perform an oxidation reaction, then opening a stirring paddle and an ultrasonic plate and continuously starting the first peristaltic pump, and introducing air into the reactor to promote the oxidation reaction;
step two, after the oxidation reaction in the step one is finished, closing the stirring paddle and the ultrasonic plate, and standing and layering the system of the oxidation reaction to obtain an upper-layer reaction acid solution and a lower-layer graphene oxide solution;
step three, opening and adjusting a three-way valve to communicate a concentrated sulfuric acid solution storage bottle with a reactor, reversely starting a first peristaltic pump, and enabling the upper layer reaction acid liquid obtained in the step two to sequentially pass through a first conveying pipe and a first conveying branch pipe to enter the concentrated sulfuric acid solution storage bottle to obtain concentrated sulfuric acid recovery liquid;
opening and adjusting a three-way valve to communicate a water/hydrogen peroxide storage bottle with the reactor and start a first peristaltic pump to enable water/hydrogen peroxide to enter the reactor, opening a stirring paddle and an ultrasonic plate, and stripping the lower-layer graphene oxide liquid obtained in the second step to obtain a stripped graphene oxide liquid;
step five, starting a second peristaltic pump, enabling the stripped graphene oxide liquid obtained in the step four to enter a second conveying pipe through a discharging pipe, and then entering a filter column of a filter for filtering and purifying to obtain a purified graphene oxide liquid;
and step six, starting a third peristaltic pump, and enabling the purified graphene oxide liquid obtained in the step five to enter a graphene oxide storage bottle through a third conveying pipe, so as to obtain graphene oxide.
The method comprises the steps of firstly, slowly adding a concentrated sulfuric acid solution into a reactor filled with graphite, slowly adding potassium permanganate into the reactor through a feeder to perform oxidation reaction, assisting ultrasonic treatment, ventilation and stirring bubbling to promote the oxidation reaction to fully separate interlayer sheets of the graphite to obtain graphene oxide, depositing the graphene oxide in a solution of a reaction system under the action of gravity, standing and layering to obtain an upper layer reaction acid solution and a lower layer graphene oxide solution, pumping out the upper layer reaction acid solution for recycling due to the fact that the main component of the upper layer reaction acid solution is concentrated sulfuric acid, adding water/hydrogen peroxide into the lower layer graphene oxide solution to generate a heat release effect, assisting stirring and ultrasonic treatment to further thermally expand and strip the graphite which is not fully oxidized in the lower layer graphene oxide solution to obtain graphene oxide, and finally sending the stripped graphene oxide solution into a filter to be filtered and purified, obtaining the purified graphene oxide solution, and further preparing the graphene oxide. According to the invention, the preparation and purification of the graphene oxide are coupled, so that the continuous preparation and purification of the graphene oxide are realized, meanwhile, the phenomenon of non-uniform oxidation reaction of graphite is avoided by respectively and slowly feeding the concentrated sulfuric acid solution and the potassium permanganate, the size uniformity of the graphene oxide is improved, the graphene oxide solution is peeled off again, the peeling time of the oxidation reaction is shortened, the yield of the graphene oxide is improved, the continuous preparation and purification efficiency of the graphene oxide is further improved, the recovery and continuous utilization of the concentrated sulfuric acid solution are realized, and the pollution and waste are avoided.
The method is characterized in that the graphite in the step one is flake graphite. The scale graphite with a better layered structure is used as a raw material, so that sulfate radicals can be more favorably inserted into the graphite layer, and the graphite layer is separated from the graphite layer after thermal expansion to obtain the graphene oxide.
The method is characterized in that in the first step, the mass concentration of the concentrated sulfuric acid solution is 98%, and the ratio of the volume of the concentrated sulfuric acid solution to the mass of the graphite to the mass of the potassium permanganate is (12.5-50): 1: (1-3), wherein the volume unit is mL, and the mass unit is g; the time of the oxidation reaction is 1-5 h. The raw material proportion ensures the smooth proceeding of the oxidation reaction, so that the graphite sheet layer is fully separated from the prepared graphene oxide, the waste caused by excessive reaction materials is avoided, the smooth proceeding of the continuous preparation process is ensured, and the time of the oxidation reaction is controlled to be 1-5 h.
The method is characterized in that the standing time in the step two is 1-2 h. Because the oxidation reaction process is assisted by ultrasound, ventilation, stirring and bubbling, the oxidation reaction is promoted to be carried out, and graphite is fully converted into graphene oxide and deposited, the upper layer reaction acid solution taking concentrated sulfuric acid as a main component and the lower layer graphene oxide solution deposited with the graphene oxide are layered through standing for the above time, so that the concentrated sulfuric acid is convenient to recover and the subsequent purification process is convenient to carry out.
Compared with the prior art, the invention has the following advantages:
1. the device for continuously preparing and purifying the graphene oxide is respectively provided with the concentrated sulfuric acid solution storage bottle connected with the reactor and the first lifting platform provided with the pore passage for communicating the feeder and the reactor, so that the concentrated sulfuric acid solution and the potassium permanganate are fed separately, the phenomenon of nonuniform oxidation reaction after the concentrated sulfuric acid solution and the potassium permanganate are directly contacted in a large amount is avoided, the size uniformity of the graphene oxide is improved, the continuous preparation of the graphene oxide and the recovery of the concentrated sulfuric acid solution are simultaneously realized, a filter is arranged behind the reactor for purifying the graphene oxide solution so as to continuously remove metal ions, the purification efficiency is high, the water resource waste is less, and the continuous preparation and purification of the graphene oxide are realized.
2. According to the continuous preparation and purification device for the graphene oxide, the water/hydrogen peroxide storage bottle connected with the reactor through the pipeline is arranged, so that the oxidized graphene liquid obtained after oxidation is stripped again, the stripping time of the oxidation reaction is shortened, the yield of the graphene oxide is improved, and the continuous preparation and purification efficiency of the graphene oxide is further improved.
3. According to the device, the ultrasonic plate is arranged right below the reactor, the first peristaltic pump is arranged to introduce air, and the stirring paddle is arranged in the reactor to perform ultrasonic and bubbling to assist in promoting the oxidation reaction and stripping again, so that the stripping of the graphite layer is further promoted, the phenomenon that the oxidation degree of the graphene oxide obtained by single stirring or ultrasonic preparation in the prior art is not uniform, and the graphene oxide floats on the reaction liquid surface and is not easily separated from the reaction acid liquid is avoided, and the preparation efficiency of the graphene oxide is improved.
4. The device disclosed by the invention realizes the separate slow feeding of the concentrated sulfuric acid solution and the potassium permanganate, avoids the violent reaction of the concentrated sulfuric acid solution and the potassium permanganate after direct large-scale contact, releases a large amount of heat and oxygen, causes the reactor to be broken due to local overheating, and ensures the safety of graphene oxide preparation because the reaction liquid is splashed out.
5. According to the method, the preparation and the purification of the graphene oxide are coupled through the separate feeding of the strong acid and the oxidant, the oxidation reaction and the stripping operation of the graphite again and the purification of the filter, so that the continuous preparation and the purification of the graphene oxide are realized, the phenomenon of uneven oxidation reaction of the graphite is avoided, the size uniformity of the graphene oxide is improved, the preparation and purification efficiency of the graphene oxide is improved, the recovery and the continuous utilization of concentrated sulfuric acid solution are realized, and the pollution and the waste are avoided.
6. According to the invention, water/hydrogen peroxide is introduced into the lower layer graphene oxide liquid obtained by the oxidation reaction to generate a heat release effect, so that the graphite which is not fully oxidized in the lower layer graphene oxide liquid is further subjected to thermal expansion stripping, and then stripping is carried out again, the yield of the graphene oxide is improved, the acid concentration in the lower layer graphene oxide liquid is reduced, and the subsequent purification process is favorably carried out smoothly; in addition, the introduced hydrogen peroxide has strong oxidizing property, so that the graphite which is not subjected to sufficient oxidation reaction in the lower graphene oxide solution can continuously generate oxidation reaction, and the yield of the graphene oxide is further improved.
7. The invention assists ultrasonic treatment and stirring in the oxidation reaction and re-stripping action, further promotes the stripping of graphene interlamination, improves the preparation speed of graphene oxide, and realizes the rapid oxidation stripping of graphene oxide.
8. According to the method, the oxidation degree of the graphite is controlled by controlling the reaction time of the oxidation reaction and adjusting the auxiliary modes in the oxidation reaction and the re-stripping operation, so that the graded controllable preparation of the graphene oxide with different thicknesses is realized, and the low-cost industrial batch preparation is easy to realize.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is a schematic structural diagram of a continuous graphene oxide preparation and purification apparatus according to the present invention.
Description of reference numerals:
1-a concentrated sulfuric acid solution storage bottle; 2-water/hydrogen peroxide storage bottle; 3-1 — a first delivery leg;
3-2-second delivery branch pipe; 3-a first delivery pipe; 4-three-way valve;
5-a first peristaltic pump; 6-a reactor; 7-a feeder;
8-stirring paddle; 9-a first lifting platform; 10, a discharge pipe;
11-ultrasonic plate; 12-a second peristaltic pump; 13-a second duct;
14-a second lifting platform; 15-a filter; 16-a filter column;
17-a third peristaltic pump; 18-a third delivery pipe; 19-graphene oxide storage bottle.
Detailed Description
The continuous preparation and purification apparatus of graphene oxide according to the present invention is described in detail in example 1.
Example 1
As shown in fig. 1, the continuous preparation and purification apparatus for graphene oxide of this embodiment includes a reactor 6, and a concentrated sulfuric acid solution storage bottle 1 and a water/hydrogen peroxide storage bottle 2 respectively connected to the reactor 6 through a delivery pipe, the delivery pipe is provided with a three-way valve 4, the concentrated sulfuric acid solution storage bottle 1 is connected to the three-way valve 4 through a first delivery branch pipe 3-1, the water/hydrogen peroxide storage bottle 2 is connected to the three-way valve 4 through a second delivery branch pipe 3-2, the reactor 6 is connected to the three-way valve 4 through a first delivery pipe 3-3, the first delivery pipe 3-3 is provided with a first peristaltic pump 5, an ultrasonic plate 11 is provided under the reactor 6, a first lifting platform 9 is provided over the reactor 6, the first lifting feeder 9 is provided with a pore channel for communicating 7 with the reactor 6, the pore that supplies stirring rake 8 and reactor 6 to communicate and the pore that supplies discharge pipe 10 and reactor 6 to communicate, discharge pipe 10 passes through the entry linkage of the filter column 16 in second conveyer pipe 13 and the filter 15, be provided with second peristaltic pump 12 on the second conveyer pipe 13, be provided with the fixed second elevating platform 14 who filters column 16 directly over the filter 15, the export of filter column 16 is connected with oxidation graphite alkene storage bottle 19 through third conveyer pipe 18, be provided with third peristaltic pump 17 on the third conveyer pipe 18.
The continuous preparation and purification device of graphene oxide is respectively provided with a concentrated sulfuric acid solution storage bottle 1 connected with a reactor 6 and a first lifting platform 9 provided with a pore passage for communicating a feeder 7 and the reactor 6, thereby feeding the concentrated sulfuric acid solution and the potassium permanganate separately, avoiding the violent action after the two are in direct contact, generating the phenomenon of uneven oxidation reaction, improving the size uniformity of the graphene oxide, realizing the continuous preparation of the graphene oxide, ensuring the safety of the preparation of the graphene oxide, the upper layer reaction acid solution obtained after the oxidation reaction can be pumped out through the first peristaltic pump 5, so that the recovery of the concentrated sulfuric acid solution is realized, a filter 15 is arranged behind the reactor 6 for purifying the graphene oxide solution so as to continuously remove metal ions, the purification efficiency is high, the waste of water resources is less, and the continuous preparation and purification of the graphene oxide are realized; according to the invention, the water/hydrogen peroxide storage bottle 2 connected with the reactor 6 through a pipeline is arranged, and the oxidized graphene liquid obtained after oxidation is stripped again by adopting water/hydrogen peroxide, so that the stripping time of the oxidation reaction is shortened, the yield of the oxidized graphene is improved, and the continuous preparation and purification efficiency of the oxidized graphene is further improved; according to the device, the ultrasonic plate is arranged right below the reactor, the first peristaltic pump is arranged to introduce air, and the stirring paddle is arranged in the reactor to perform ultrasonic and bubbling to assist in promoting the oxidation reaction and stripping again, so that stripping of a graphite layer is further promoted, the phenomenon that graphene oxide obtained by ultrasonic preparation in the prior art floats on the reaction liquid surface and is not easily separated from reaction acid liquor is avoided, and the preparation efficiency of the graphene oxide is improved.
The method for preparing graphene oxide according to the present invention is described in detail in examples 2 to 4.
Example 2
The preparation method of graphene oxide of the embodiment includes the following steps:
step one, filling 250mL of concentrated sulfuric acid solution with the mass concentration of 98% into a concentrated sulfuric acid solution storage bottle 1, filling water into a water/hydrogen peroxide storage bottle 2, filling 5g of flake graphite into a reactor 6, opening and adjusting a three-way valve 4 to communicate the concentrated sulfuric acid solution storage bottle 1 with the reactor 6 and starting a first peristaltic pump 5, so that the 250mL of concentrated sulfuric acid solution completely enters the reactor 6, then adding 15g of potassium permanganate serving as an oxidant into the reactor 6 through a feeder 7 to perform oxidation reaction for 1h, then opening a stirring paddle 8 and an ultrasonic plate 11 and continuously starting the first peristaltic pump 5, introducing air into the reactor 6, and promoting the oxidation reaction to be performed;
step two, after the oxidation reaction in the step one is finished, closing the stirring paddle 8 and the ultrasonic plate 11, and standing and layering the system of the oxidation reaction for 1 hour to obtain an upper layer reaction acid solution and a lower layer graphene oxide solution;
step three, opening and adjusting a three-way valve 4 to communicate a concentrated sulfuric acid solution storage bottle 1 with a reactor 6, reversely starting a first peristaltic pump 5, and enabling the upper layer reaction acid solution obtained in the step two to sequentially pass through a first conveying pipe 3-3 and a first conveying branch pipe 3-1 to enter a concentrated sulfuric acid solution storage bottle 1 to obtain a concentrated sulfuric acid recovery solution;
opening and adjusting a three-way valve 4 to connect a water/hydrogen peroxide storage bottle 2 with a reactor 6 and start a first peristaltic pump 5 to enable water to enter the reactor 6, opening a stirring paddle 8 and an ultrasonic plate 11, and stripping the lower layer graphene oxide liquid obtained in the second step to obtain a stripped graphene oxide liquid;
step five, starting a second peristaltic pump 12, enabling the stripped graphene oxide liquid obtained in the step four to enter a second conveying pipe 13 through a discharging pipe 10, and then entering a filter column 16 of a filter 15 for filtering and purifying to obtain a purified graphene oxide liquid;
and step six, starting a third peristaltic pump 17, so that the purified graphene oxide liquid obtained in the step five enters a graphene oxide storage bottle 19 through a third conveying pipe 18, and further graphene oxide is obtained.
Through detection, all the flake graphite in the embodiment is converted into the graphene oxide, the single-layer rate of the graphene oxide reaches 95%, the thickness of the graphene oxide is 0.8nm, and the graphene oxide has good uniformity.
Example 3
The preparation method of graphene oxide of the embodiment includes the following steps:
step one, filling 250mL of concentrated sulfuric acid solution with the mass concentration of 98% into a concentrated sulfuric acid solution storage bottle 1, filling hydrogen peroxide into a water/hydrogen peroxide storage bottle 2, filling 20g of flake graphite into a reactor 6, opening and adjusting a three-way valve 4 to communicate the concentrated sulfuric acid solution storage bottle 1 with the reactor 6 and start a first peristaltic pump 5, so that the 250mL of concentrated sulfuric acid solution completely enters the reactor 6, then adding 20g of potassium permanganate serving as an oxidant into the reactor 6 through a feeder 7 to perform oxidation reaction for 5 hours, then opening a stirring paddle 8 and an ultrasonic plate 11 and continuously starting the first peristaltic pump 5, introducing air into the reactor 6, and promoting the oxidation reaction to be performed;
step two, after the oxidation reaction in the step one is finished, closing the stirring paddle 8 and the ultrasonic plate 11, and standing and layering the system of the oxidation reaction for 2 hours to obtain an upper-layer reaction acid solution and a lower-layer graphene oxide solution;
step three, opening and adjusting a three-way valve 4 to communicate a concentrated sulfuric acid solution storage bottle 1 with a reactor 6, reversely starting a first peristaltic pump 5, and enabling the upper layer reaction acid solution obtained in the step two to sequentially pass through a first conveying pipe 3-3 and a first conveying branch pipe 3-1 to enter a concentrated sulfuric acid solution storage bottle 1 to obtain a concentrated sulfuric acid recovery solution;
opening and adjusting a three-way valve 4 to connect the water/hydrogen peroxide storage bottle 2 with the reactor 6 and start a first peristaltic pump 5 to enable hydrogen peroxide to enter the reactor 6, opening a stirring paddle 8 and an ultrasonic plate 11, and stripping the lower layer graphene oxide liquid obtained in the second step to obtain a stripped graphene oxide liquid;
step five, starting a second peristaltic pump 12, enabling the stripped graphene oxide liquid obtained in the step four to enter a second conveying pipe 13 through a discharging pipe 10, and then entering a filter column 16 of a filter 15 for filtering and purifying to obtain a purified graphene oxide liquid;
and step six, starting a third peristaltic pump 17, so that the purified graphene oxide liquid obtained in the step five enters a graphene oxide storage bottle 19 through a third conveying pipe 18, and further graphene oxide is obtained.
Through detection, all the flake graphite in the embodiment is converted into the graphene oxide, the single-layer rate of the graphene oxide reaches 90%, the thickness of the graphene oxide is 0.9nm, and the graphene oxide has good uniformity.
Example 4
The preparation method of graphene oxide of the embodiment includes the following steps:
step one, filling 250mL of concentrated sulfuric acid solution with the mass concentration of 98% into a concentrated sulfuric acid solution storage bottle 1, filling water into a water/hydrogen peroxide storage bottle 2, filling 10g of flake graphite into a reactor 6, opening and adjusting a three-way valve 4 to communicate the concentrated sulfuric acid solution storage bottle 1 with the reactor 6 and starting a first peristaltic pump 5, so that the 250mL of concentrated sulfuric acid solution completely enters the reactor 6, then adding 20g of potassium permanganate serving as an oxidant into the reactor 6 through a feeder 7 to perform oxidation reaction for 3.5 hours, then opening a stirring paddle 8 and an ultrasonic plate 11 and continuously starting the first peristaltic pump 5, introducing air into the reactor 6, and promoting the oxidation reaction to be performed;
step two, after the oxidation reaction in the step one is finished, closing the stirring paddle 8 and the ultrasonic plate 11, and standing and layering the system of the oxidation reaction for 1.5 hours to obtain an upper-layer reaction acid solution and a lower-layer graphene oxide solution;
step three, opening and adjusting a three-way valve 4 to communicate a concentrated sulfuric acid solution storage bottle 1 with a reactor 6, reversely starting a first peristaltic pump 5, and enabling the upper layer reaction acid solution obtained in the step two to sequentially pass through a first conveying pipe 3-3 and a first conveying branch pipe 3-1 to enter a concentrated sulfuric acid solution storage bottle 1 to obtain a concentrated sulfuric acid recovery solution;
opening and adjusting a three-way valve 4 to connect a water/hydrogen peroxide storage bottle 2 with a reactor 6 and start a first peristaltic pump 5 to enable water to enter the reactor 6, opening a stirring paddle 8 and an ultrasonic plate 11, and stripping the lower layer graphene oxide liquid obtained in the second step to obtain a stripped graphene oxide liquid;
step five, starting a second peristaltic pump 12, enabling the stripped graphene oxide liquid obtained in the step four to enter a second conveying pipe 13 through a discharging pipe 10, and then entering a filter column 16 of a filter 15 for filtering and purifying to obtain a purified graphene oxide liquid;
and step six, starting a third peristaltic pump 17, so that the purified graphene oxide liquid obtained in the step five enters a graphene oxide storage bottle 19 through a third conveying pipe 18, and further graphene oxide is obtained.
Through detection, all the flake graphite in the embodiment is converted into the graphene oxide, the single-layer rate of the graphene oxide reaches 95%, the thickness of the graphene oxide is 0.9nm, and the graphene oxide has good uniformity.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (5)
1. The continuous preparation and purification device for the graphene oxide is characterized by comprising a reactor (6), a concentrated sulfuric acid solution storage bottle (1) and a water/hydrogen peroxide solution storage bottle (2) which are respectively connected with the reactor (6) through a conveying pipe, wherein a three-way valve (4) is arranged on the conveying pipe, the concentrated sulfuric acid solution storage bottle (1) is connected with the three-way valve (4) through a first conveying branch pipe (3-1), the water/hydrogen peroxide solution storage bottle (2) is connected with the three-way valve (4) through a second conveying branch pipe (3-2), the reactor (6) is connected with the three-way valve (4) through a first conveying pipe (3-3), a first peristaltic pump (5) is arranged on the first conveying pipe (3-3), an ultrasonic plate (11) is arranged under the reactor (6), a first lifting platform (9) is arranged right above the reactor (6), offer the pore that supplies feeder (7) and reactor (6) to communicate on first elevating platform (9) respectively, supply the pore of stirring rake (8) and reactor (6) intercommunication and supply discharge pipe (10) and the pore of reactor (6) intercommunication, discharge pipe (10) are through the entry linkage of filter column (16) in second conveyer pipe (13) and filter (15), be provided with second peristaltic pump (12) on second conveyer pipe (13), be provided with second elevating platform (14) of fixed filter column (16) directly over filter (15), the export of filter column (16) is passed through third conveyer pipe (18) and is connected with oxidation graphite alkene storage bottle (19), be provided with third peristaltic pump (17) on third conveyer pipe (18).
2. A method for preparing graphene oxide using the apparatus for continuously preparing and purifying graphene oxide according to claim 1, comprising the steps of:
step one, filling a concentrated sulfuric acid solution into a concentrated sulfuric acid solution storage bottle (1), filling water/hydrogen peroxide into a water/hydrogen peroxide storage bottle (2), filling graphite into a reactor (6), opening and adjusting a three-way valve (4) to communicate the concentrated sulfuric acid solution storage bottle (1) with the reactor (6) and start a first peristaltic pump (5) to enable the concentrated sulfuric acid solution to completely enter the reactor (6), then adding an oxidant potassium permanganate into the reactor (6) through a feeder (7) to perform an oxidation reaction, then opening a stirring paddle (8) and an ultrasonic plate (11) and continuously starting the first peristaltic pump (5), introducing air into the reactor (6) to promote the oxidation reaction;
step two, after the oxidation reaction in the step one is finished, closing the stirring paddle (8) and the ultrasonic plate (11), and standing and layering the system of the oxidation reaction to obtain an upper-layer reaction acid solution and a lower-layer graphene oxide solution;
step three, opening and adjusting a three-way valve (4) to communicate a concentrated sulfuric acid solution storage bottle (1) with a reactor (6), reversely starting a first peristaltic pump (5), and enabling the upper layer reaction acid liquid obtained in the step two to sequentially pass through a first conveying pipe (3-3) and a first conveying branch pipe (3-1) to enter the concentrated sulfuric acid solution storage bottle (1) to obtain concentrated sulfuric acid recovery liquid;
opening and adjusting a three-way valve (4) to connect a water/hydrogen peroxide storage bottle (2) and a reactor (6) and start a first peristaltic pump (5) to enable water/hydrogen peroxide to enter the reactor (6), opening a stirring paddle (8) and an ultrasonic plate (11), and stripping the lower-layer graphene oxide liquid obtained in the second step to obtain a stripped graphene oxide liquid;
step five, starting a second peristaltic pump (12), enabling the stripped graphene oxide liquid obtained in the step four to enter a second conveying pipe (13) through a discharging pipe (10), and then entering a filtering column (16) of a filter (15) for filtering and purifying to obtain a purified graphene oxide liquid;
and step six, starting a third peristaltic pump (17) to enable the purified graphene oxide liquid obtained in the step five to enter a graphene oxide storage bottle (19) through a third conveying pipe (18) so as to obtain graphene oxide.
3. The method of claim 2, wherein in step one the graphite is flake graphite.
4. The method according to claim 2, wherein the mass concentration of the concentrated sulfuric acid solution in the first step is 98%, and the ratio of the volume of the concentrated sulfuric acid solution to the mass of graphite to the mass of potassium permanganate is (12.5-50): 1: (1-3), wherein the volume unit is mL, and the mass unit is g; the time of the oxidation reaction is 1-5 h.
5. The method according to claim 2, wherein the standing time in the second step is 1 to 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910701163.5A CN110342506B (en) | 2019-07-31 | 2019-07-31 | Continuous preparation and purification device and method for graphene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910701163.5A CN110342506B (en) | 2019-07-31 | 2019-07-31 | Continuous preparation and purification device and method for graphene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110342506A CN110342506A (en) | 2019-10-18 |
| CN110342506B true CN110342506B (en) | 2021-05-25 |
Family
ID=68183512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910701163.5A Active CN110342506B (en) | 2019-07-31 | 2019-07-31 | Continuous preparation and purification device and method for graphene oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110342506B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2019
- 2019-07-31 CN CN201910701163.5A patent/CN110342506B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110342506A (en) | 2019-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Highly conductive graphene/PANi-phytic acid modified cathodic filter membrane and its antifouling property in EMBR in neutral conditions | |
| KR101652965B1 (en) | Manufacturing method of graphene oxide using ultrasonication and apparatus for the same | |
| KR101573358B1 (en) | Nature-friendly graphene oxide manufaturing system using couette-taylor reactor | |
| CN104649253A (en) | Preparing methods of porous graphene and porous graphene film | |
| CN105126742B (en) | A kind of method using modified kaolin sorbent treatment fluoride waste | |
| CN103122465B (en) | Preparation method of flaky metal powder | |
| CN105585003B (en) | A kind of large-scale continuous preparation method and its equipment of graphene oxide and graphene nanometer sheet | |
| CN101875491A (en) | Green preparation method of graphene based on tea polyphenol/green tea juice | |
| CN104148666A (en) | Method for modifying graphene through nano-sliver | |
| CN201762209U (en) | Integrally combined device for recycling coking wastewater | |
| CN103864059A (en) | Graphene high-efficiency preparation method based on extraction purification technology | |
| KR20150096899A (en) | Graphene oxide manufaturing system using couette-taylor reactor and method thereof | |
| CN103031578B (en) | A kind of electrolytic method producing nickel foil | |
| CN105314623A (en) | Graphene synthesis method | |
| CN114572969A (en) | Microfluidic reaction system and method for preparing reduced graphene oxide | |
| CN115057435B (en) | Method for preparing graphene oxide by recycling concentrated sulfuric acid and application of product obtained by method | |
| CN110342506B (en) | Continuous preparation and purification device and method for graphene oxide | |
| CN103232326A (en) | Continuous production process for preparing phenol by benzene hydroxylation | |
| CN105129757A (en) | Method for preparing battery grade iron phosphate through chemical nickel-plating waste liquid | |
| CN206033425U (en) | A processing apparatus for phosphorous sour waste water | |
| CN105032352B (en) | A kind of method of one pot process magnetic 3D graphene composite adsorbing materials | |
| CN108975316B (en) | Preparation method of graphene film | |
| CN103848419B (en) | Method for preparing ultrafine graphite oxide by membrane process washing separation | |
| CN114195140B (en) | Method for preparing controllable graphene by electrode and magnetic field regulation ion intercalation | |
| CN115275217A (en) | Semi-continuous core-shell structure catalyst preparation device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |