CN113213469B - Equipment for preparing uniform small-size graphene oxide - Google Patents
Equipment for preparing uniform small-size graphene oxide Download PDFInfo
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- CN113213469B CN113213469B CN202110599868.8A CN202110599868A CN113213469B CN 113213469 B CN113213469 B CN 113213469B CN 202110599868 A CN202110599868 A CN 202110599868A CN 113213469 B CN113213469 B CN 113213469B
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
Abstract
The invention discloses equipment for preparing uniform small-size graphene oxide, which consists of an intercalation reaction kettle, an oxidation reaction kettle and a collection kettle, wherein the intercalation reaction kettle is arranged in the oxidation reaction kettle; the side wall of the intercalation reaction kettle is provided with a first hole, the side wall of the oxidation reaction kettle is provided with a second hole, the diameter of the first hole is 20-80 microns, and the diameter of the second hole is 4-20 microns; the device is characterized in that a stirrer is arranged in the intercalation reaction kettle, shearing emulsifying machines are respectively arranged in the intercalation reaction kettle and the oxidation reaction kettle, and a discharge valve is arranged at the bottom of the collection kettle. According to the invention, through two-stage size screening and two-stage shearing, the sizes of the graphene oxide are uniformly distributed in a very narrow size range, the problem of wide distribution of the graphene oxide obtained by the existing production technology is solved, and meanwhile, the method is low in cost, small in industrialization difficulty and has a remarkable practical value.
Description
Technical Field
The invention belongs to the field of equipment for preparing graphene oxide, and particularly relates to equipment for preparing uniform small-size graphene oxide.
Background
Graphene is a star material in the 21 st century and has received a great deal of attention since its appearance. Due to unique characteristics of mechanics, thermal, electricity, optics, magnetism, biology and the like, the material is used in the fields of structural materials, heat conduction elements, conductive agents, LEDs, optoelectronic chips, composite materials, biological medicines and the like. However, graphene itself is easily difficult to prepare, and graphene prepared by a Chemical Vapor Deposition (CVD) method has a perfect two-dimensional structure, but is easily defective in subsequent transfer and use processes, and is difficult to mass-produce and unsuitable for industrial application. In contrast, graphene Oxide (GO) as an important graphene derivative material can be prepared simply and rapidly in batches by oxidation stripping of graphite, can be directly used for blending to prepare a composite material, can be assembled to obtain different dimensional materials such as graphene fibers, graphene aerogel and graphene films, and can restore the conjugated structure of graphene after reduction. Therefore, graphene oxide is a preferred solution for realizing mass production of graphene.
The conventional preparation of graphene oxide is carried out by improving a Hummers method, graphite and potassium permanganate react in a concentrated sulfuric acid environment by adopting single-kettle low-temperature oxidation, and after the reaction is finished, the water-phase dispersion liquid of the graphene oxide is obtained by water washing and concentration. However, the method has the problem of wide size distribution, because in the process of completely oxidizing graphite, small-diameter graphite is firstly oxidized, while large-diameter graphite can be oxidized for a longer time, and during the process, the small-diameter graphite is further oxidized in the plane, so that small-diameter graphene oxide is further fragmented, and when the whole reaction is finished, the size distribution of graphene oxide in the system is very wide, and the whole reaction time is too long.
Therefore, an apparatus for preparing uniform small-sized graphene oxide is required.
Disclosure of Invention
The invention aims to provide equipment for preparing graphene oxide with uniform and small size aiming at the defects of the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the equipment for preparing the uniform small-size graphene oxide is characterized by comprising an intercalation reaction kettle, an oxidation reaction kettle and a collection kettle, wherein the intercalation reaction kettle is arranged in the oxidation reaction kettle, and the oxidation reaction kettle is arranged in the collection kettle; the side wall of the intercalation reaction kettle is provided with a first hole, the side wall of the oxidation reaction kettle is provided with a second hole, the diameter of the first hole is 20-80 microns, and the diameter of the second hole is 4-20 microns; the stirrer is arranged in the intercalation reaction kettle, the shearing emulsifying machine is respectively arranged in the intercalation reaction kettle and the oxidation reaction kettle, and the discharge valve is arranged at the bottom of the collecting kettle.
Furthermore, the bottom of the oxidation reaction kettle is connected with a pipeline returning to the intercalation reaction kettle, and the pipeline is provided with a delivery pump.
Furthermore, the diameter of the first hole is 40 micrometers, and the diameter of the second hole is 10 micrometers.
Further, the diameter of the first hole is 20 micrometers, and the diameter of the second hole is 4 micrometers.
Further, the diameter of the first hole is 80 micrometers, and the diameter of the second hole is 20 micrometers.
Furthermore, a plurality of baffles with an included angle of 10-30 degrees with the horizontal direction are arranged on the peripheries of the first hole and the second hole.
The side wall of the intercalation reaction kettle and the side wall of the oxidation reaction kettle can be made of punching plates or multi-layer silk screens.
Compared with the prior art, the invention has the beneficial effects that:
(1) Graphite and concentrated sulfuric acid are mixed and then added into an intercalation reaction kettle, under the stirring and shearing action, the graphite is intercalated by sulfuric acid to form intercalated graphite, and under the shearing force action, large-size intercalated graphite is torn into small-size graphite, so that primary homogenization is realized. After the reacted intercalated graphite is screened by the holes on the side wall of the reaction kettle, most of the intercalated graphite meeting the size requirement enters an oxidation reaction kettle, and the reaction and the shearing are continuously carried out when the residual size does not meet the requirement. The intercalated graphite entering the oxidation reaction kettle is oxidized and stripped under the action of an oxidant, size homogenization and stripping are further realized under the shearing action, the graphite oxide meeting the size requirement after reaction enters a collection kettle through holes, and the reaction continues if the residual graphite is not completely reacted. And collecting the graphite oxide in the kettle, and then washing, separating, concentrating and the like to obtain the graphene oxide with uniform small size.
(2) Residual intercalated graphite which is not completely reacted in the oxidation kettle is thrown into the intercalation reaction kettle again through the pump delivery, and a new round of reaction is carried out with a new batch of subsequent mixed liquid of graphite and concentrated sulfuric acid, so that 100% of materials can be utilized, raw material waste is avoided, and pollution is avoided.
(3) The shearing equipment in the intercalation reaction kettle mainly aims to tear the large-size graphite and the intercalation graphite through shearing force to enable the sizes to be more uniform, and the shearing equipment in the oxidation reaction kettle mainly utilizes the shearing force to accelerate stripping of the graphite oxide and simultaneously tears the large-size graphite oxide to enable the size of the obtained graphite oxide to be uniform.
(4) The diameter of the holes on the wall of the intercalation reaction kettle is generally about 1/2 to 1/5 of that of graphite, and the diameter of the holes on the wall of the oxidation reaction kettle is generally about 1/10 to 1/50 of that of the graphite.
(5) Set up the baffle on the cauldron wall, when there is certain contained angle between baffle and horizontal direction, along stirring and the mixed liquid of doing the screw action forms little torrent in baffle department to bring extra shearing force, make graphite oxide torn again before getting into the hole, thereby further reduce the size. After the steps, the large-size graphite oxide can be rapidly reduced to the diameter of the hole.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for preparing graphene oxide with uniform small size according to the present invention;
FIG. 2 is a schematic structural diagram of another apparatus for preparing graphene oxide with uniform small size according to the present invention;
fig. 3 is a schematic structural diagram of holes and baffles of an apparatus for preparing graphene oxide with uniform small size according to the present invention.
Wherein: intercalation reation kettle 1, oxidation reation kettle 2, collection cauldron 3, intercalation reation kettle lateral wall 4, oxidation reation kettle lateral wall 5, agitator 6, shearing emulsion machine 7, bleeder valve 8, delivery pump 9.
Detailed Description
Example 1
As shown in fig. 1, an apparatus for preparing graphene oxide of uniform small size comprises an intercalation reaction kettle 1, an oxidation reaction kettle 2 and a collection kettle 3, wherein the intercalation reaction kettle 1 is installed inside the oxidation reaction kettle 2, and the oxidation reaction kettle 2 is installed inside the collection kettle 3; the side wall 4 of the intercalation reaction kettle is provided with a first hole, the side wall 5 of the oxidation reaction kettle is provided with a second hole, the diameter of the first hole is 40 microns, and the diameter of the second hole is 10 microns; a stirrer 6 is arranged in the intercalation reaction kettle 1, a shearing emulsifying machine 7 is respectively arranged in the intercalation reaction kettle 1 and the oxidation reaction kettle 2, and a discharge valve 8 is arranged at the bottom of the collection kettle 3. The side wall 4 of the intercalation reaction kettle and the side wall 5 of the oxidation reaction kettle are made of punching plates.
Through the equipment of the embodiment, the following method can be realized to prepare the graphene oxide with the size uniformly distributed about 10 microns. The method specifically comprises the following steps:
a method of preparing uniform small-sized graphene oxide, comprising:
adding a mixed solution of graphite and concentrated sulfuric acid into an intercalation reaction kettle 1, and stirring while carrying out a shearing reaction, wherein the size of the graphite is about 100 micrometers, and the mass ratio of the graphite to the concentrated sulfuric acid is 1;
adding a mixed solution of an oxidant and concentrated sulfuric acid into an oxidation reaction kettle 2, and reacting under shearing, wherein the oxidant is potassium permanganate, and the ratio of graphite to the oxidant is 1;
and after 8 hours of reaction, stopping stirring and shearing, opening a discharge valve 8 of the collection kettle 3, and performing subsequent washing, separation and concentration to obtain the graphene oxide with the size uniformly distributed about 10 microns.
Adding materials into the intercalation reaction kettle 1 and the oxidation reaction kettle 2 again, and repeating the steps.
Example 2
As shown in fig. 1, an apparatus for preparing graphene oxide with uniform small size comprises an intercalation reaction kettle 1, an oxidation reaction kettle 2 and a collection kettle 3, wherein the intercalation reaction kettle 1 is installed inside the oxidation reaction kettle 2, and the oxidation reaction kettle 2 is installed inside the collection kettle 3; the side wall 4 of the intercalation reaction kettle is provided with a first hole, the side wall 5 of the oxidation reaction kettle is provided with a second hole, the diameter of the first hole is 20 micrometers, and the diameter of the second hole is 4 micrometers; a stirrer 6 is arranged in the intercalation reaction kettle 1, a shearing emulsifying machine 7 is respectively arranged in the intercalation reaction kettle 1 and the oxidation reaction kettle 2, and a discharge valve 8 is arranged at the bottom of the collection kettle 3. The side wall 4 of the intercalation reaction kettle and the side wall 5 of the oxidation reaction kettle are made of multilayer silk screens.
By the equipment of the embodiment, the following method can be realized for preparing the graphene oxide with the size uniformly distributed about 4 microns. The method specifically comprises the following steps:
a method of preparing uniform small-sized graphene oxide, comprising:
adding a mixed solution of graphite and concentrated sulfuric acid into an intercalation reaction kettle 1, and stirring while performing a shearing reaction, wherein the size of the graphite is about 50 microns, and the mass ratio of the graphite to the concentrated sulfuric acid is 1;
adding a mixed solution of an oxidant and concentrated sulfuric acid into an oxidation reaction kettle 2, and reacting under shearing, wherein the oxidant is potassium permanganate, and the ratio of graphite to the oxidant is 1;
and after the reaction is basically finished after 6.5 hours, stopping stirring and shearing, opening a discharge valve 8 of the collection kettle 3, and carrying out subsequent washing, separation and concentration to obtain the graphene oxide with the size uniformly distributed about 4 micrometers.
Adding materials into the intercalation reaction kettle 1 and the oxidation reaction kettle 2 again, and repeating the steps.
Example 3
As shown in fig. 2-3, an apparatus for preparing graphene oxide of uniform small size comprises an intercalation reaction kettle 1, an oxidation reaction kettle 2 and a collection kettle 3, wherein the intercalation reaction kettle 1 is installed inside the oxidation reaction kettle 2, and the oxidation reaction kettle 2 is installed inside the collection kettle 3; the side wall 4 of the intercalation reaction kettle is provided with a first hole, the side wall 5 of the oxidation reaction kettle is provided with a second hole, the diameter of the first hole is 80 microns, and the diameter of the second hole is 20 microns; a stirrer 6 is arranged in the intercalation reaction kettle 1, a shearing emulsifying machine 7 is respectively arranged in the intercalation reaction kettle 1 and the oxidation reaction kettle 2, and a discharge valve 8 is arranged at the bottom of the collection kettle 3; the bottom of the oxidation reaction kettle 2 is connected with a pipeline returning to the intercalation reaction kettle 1, and the pipeline is provided with a delivery pump 9. The side wall 4 of the intercalation reaction kettle is made of a punching plate, and the side wall 5 of the oxidation reaction kettle is made of a multilayer silk screen.
Through the equipment of the embodiment, the following method can be realized to prepare the graphene oxide with the size uniformly distributed about 20 microns. The method specifically comprises the following steps:
a method of preparing uniform small-sized graphene oxide, comprising:
adding a mixed solution of graphite and concentrated sulfuric acid into an intercalation reaction kettle 1, and stirring while carrying out a shearing reaction, wherein the size of the graphite is about 100 micrometers, and the mass ratio of the graphite to the concentrated sulfuric acid is 1;
adding a mixed solution of an oxidant and concentrated sulfuric acid into an oxidation reaction kettle 2, and reacting under shearing, wherein the oxidant is potassium permanganate, and the ratio of graphite to the oxidant is 1;
and after 5 hours of reaction, basically finishing stirring and shearing, opening a discharge valve 8 of the collection kettle 3, and carrying out subsequent washing, separation and concentration to obtain the graphene oxide with the size uniformly distributed about 20 micrometers.
After 5 hours of reaction, the stirring and shearing are stopped, and the mixed solution in the oxidation reaction kettle 2 is sent back to the intercalation reaction kettle 1 by using a delivery pump 9. And opening a discharge valve 8 of the collection kettle 3, and performing subsequent washing, separation and concentration to obtain the graphene oxide with the size uniformly distributed about 20 microns.
Adding materials into the intercalation reaction kettle 1 and the oxidation reaction kettle 2 again, and repeating the steps.
In this embodiment, a certain included angle exists between the first baffle and the second baffle and the horizontal direction, and the mixed liquid which performs a spiral action along the stirring forms a micro-turbulence at the baffles, so as to bring extra shearing force, so that the graphite oxide is torn again before entering the holes, and the size is further reduced. After the steps, the large-size graphite oxide can be rapidly reduced to the size of the hole diameter.
Claims (5)
1. The equipment for preparing the uniform small-size graphene oxide is characterized by comprising an intercalation reaction kettle, an oxidation reaction kettle and a collection kettle, wherein the intercalation reaction kettle is arranged in the oxidation reaction kettle, and the oxidation reaction kettle is arranged in the collection kettle; the side wall of the intercalation reaction kettle is provided with a first hole, the side wall of the oxidation reaction kettle is provided with a second hole, the diameter of the first hole is 20-80 microns, and the diameter of the second hole is 4-20 microns; a stirrer is arranged in the intercalation reaction kettle, a shearing emulsifying machine is respectively arranged in the intercalation reaction kettle and the oxidation reaction kettle, and a discharge valve is arranged at the bottom of the collection kettle; the periphery of the first hole and the second hole is provided with a plurality of baffles which form an included angle of 10-30 degrees with the horizontal direction.
2. The apparatus for preparing graphene oxide with uniform and small size according to claim 1, wherein a pipe returning to the intercalation reaction kettle is connected to the bottom of the oxidation reaction kettle, and the pipe is provided with a delivery pump.
3. The apparatus of claim 1 or 2, wherein the first holes have a diameter of 40 microns and the second holes have a diameter of 10 microns.
4. The apparatus of claim 1 or 2, wherein the first holes have a diameter of 20 microns and the second holes have a diameter of 4 microns.
5. The apparatus of claim 1 or 2, wherein the first holes have a diameter of 80 microns and the second holes have a diameter of 20 microns.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370283A (en) * | 2014-10-23 | 2015-02-25 | 江阴碳谷科技有限公司 | Graphene stripping kettle, graphene production system and graphene production method |
| CN206296037U (en) * | 2016-12-08 | 2017-07-04 | 成都新柯力化工科技有限公司 | A kind of homogeneous cutter for preparation of industrialization grapheme material |
| CN206666138U (en) * | 2016-12-08 | 2017-11-24 | 成都新柯力化工科技有限公司 | A kind of high-speed stirred stripping prepares the device of grapheme material |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201326036A (en) * | 2011-12-27 | 2013-07-01 | Ind Tech Res Inst | Methods of forming graphene |
| CN202478833U (en) * | 2012-03-08 | 2012-10-10 | 山东滨州博莱威生物技术有限公司 | Emulsifier |
| WO2016090481A1 (en) * | 2014-12-09 | 2016-06-16 | Bozalina Marie | Large scale production of oxidized graphene |
| CN204307631U (en) * | 2014-12-16 | 2015-05-06 | 济南航晨生物科技有限公司 | A kind ofly extract the special reactor of marine alga intermediate |
| TWI564244B (en) * | 2014-12-25 | 2017-01-01 | 國立臺灣師範大學 | Equipment for making graphene and its making method |
| CN105293477B (en) * | 2015-11-13 | 2017-11-14 | 安徽易能新材料科技有限公司 | A kind of preparation method of big lamella graphene oxide |
| CN105293476B (en) * | 2015-11-16 | 2018-07-10 | 复旦大学 | A kind of preparation method of large scale graphene oxide or graphene |
| JP6784458B2 (en) * | 2015-12-14 | 2020-11-11 | バオシャン アイアン アンド スティール カンパニー リミテッド | Graphene oxide and its manufacturing method |
| US20170282324A1 (en) * | 2016-03-31 | 2017-10-05 | Peter Vincent Lier | Two Stage Stainless Steel Media Sifter |
| CN105819438B (en) * | 2016-05-06 | 2018-04-17 | 成都新柯力化工科技有限公司 | A kind of method using aquashear prepare with scale nano-graphene material |
| CN108862268B (en) * | 2018-09-13 | 2019-04-02 | 常州恒利宝纳米新材料科技有限公司 | A kind of macro preparation device and method of carboxyl-functional graphene |
| CN112010298A (en) * | 2020-08-14 | 2020-12-01 | 兰州大学 | Method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide |
| CN115784217A (en) * | 2020-12-28 | 2023-03-14 | 中国科学技术大学先进技术研究院 | Method for preparing monolayer graphene oxide with controllable sheet diameter size |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370283A (en) * | 2014-10-23 | 2015-02-25 | 江阴碳谷科技有限公司 | Graphene stripping kettle, graphene production system and graphene production method |
| CN206296037U (en) * | 2016-12-08 | 2017-07-04 | 成都新柯力化工科技有限公司 | A kind of homogeneous cutter for preparation of industrialization grapheme material |
| CN206666138U (en) * | 2016-12-08 | 2017-11-24 | 成都新柯力化工科技有限公司 | A kind of high-speed stirred stripping prepares the device of grapheme material |
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