CN108689403A - The method that supercritical fluid auxiliary prepares expansible graphite - Google Patents
The method that supercritical fluid auxiliary prepares expansible graphite Download PDFInfo
- Publication number
- CN108689403A CN108689403A CN201811001945.XA CN201811001945A CN108689403A CN 108689403 A CN108689403 A CN 108689403A CN 201811001945 A CN201811001945 A CN 201811001945A CN 108689403 A CN108689403 A CN 108689403A
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- China
- Prior art keywords
- acid
- graphite
- supercritical fluid
- oxidant
- expansible graphite
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- 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of methods that supercritical fluid auxiliary prepares expansible graphite.The method includes:Mixture comprising graphite raw material and acid or acid anhydrides is placed in sealing reactor;Supercritical fluid is injected into the mixture to supercriticality, and carries out intercalation, obtains expansible graphite, the pressure of the reaction is 4~20Mpa, and temperature is 5~45 DEG C, and the time is 0.2~3h.Supercritical fluid auxiliary provided by the invention prepares the method for expansible graphite using supercritical fluid as solvent, auxiliary intercalation prepares expansible graphite, effectively improve the utilization ratio of acid and oxidant, the utilization ratio of acid and oxidant is promoted 3 times or more, less than 5%, utilization ratio can be promoted to 15% or more by method provided by the invention for traditional handicraft acid and oxidant utilization ratio under same expansion multiplying power.The dosage of acid and oxidant can be reduced about 70% by the dosage for substantially reducing acid and oxidant in traditional processing technology under the conditions of same expansion multiplying power.
Description
Technical field
The present invention relates to a kind of preparation method of expansible graphite, more particularly to prepared by a kind of supercritical fluid auxiliary can be swollen
The method of swollen graphite belongs to graphite finishing technology field.
Background technology
Expansible graphite is a kind of compound between graphite layers.Graphite crystal has the galvanized hexagonal wire mesh plane layer being made of carbon
Shape structure is combined by weaker Van der Waals force between lamella, under suitable condition, can a variety of chemical substances be inserted into graphite
Interlayer forms compound between graphite layers.When being heated to proper temperature, volume highest can expand rapidly compound between graphite layers
To 400 times.
It is about the 3~6 of graphite powder that conventionally produced expansible graphite, which must use a large amount of concentrated sulfuric acids and nitric acid, sour dosage,
Times.The use of a large amount of acid can threaten to environment, can also increase production cost.It is found by weighing, what is obtained after intercalation can
Expanded graphite weight merely adds 10%, i.e., the substance that effective intercalation enters graphite layers only has the 10% of graphite own wt.Acid
Utilization rate be less than 5%, remaining most of acid plays solvent.As can promoting the utilization rate of acid, production will be greatly reduced
Sour dosage in the process reduces the threat to environment, while reducing life to reduce the generation and discharge of spent acid in production process
Produce cost.
Invention content
The main purpose of the present invention is to provide a kind of methods that supercritical fluid auxiliary prepares expansible graphite, to overcome
The deficiencies in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
An embodiment of the present invention provides a kind of methods that supercritical fluid auxiliary prepares expansible graphite comprising:
Mixture comprising graphite raw material and acid or acid anhydrides is placed in sealing reactor;
Supercritical fluid is injected into the mixture to supercriticality, and carries out intercalation, is obtained and be may expand stone
The pressure of ink, the reaction is 4~20Mpa, and temperature is 5~45 DEG C, and the time is 0.2~3h.
Further, the intercalation carries out under conditions of to hybrid reaction system prolonged agitation.
Further, the method further includes:After the intercalation, the pressure in reactor will be sealed
It is down to normal pressure, reaction product is washed to neutrality, most obtains expansible graphite after drying process afterwards.
Further, 50~80 DEG C of the temperature of the drying process, the time be 6~for 24 hours.
In some more specific embodiment, the method further includes:Will include graphite raw material, acid or acid anhydrides with
The mixture of oxidant is placed in sealing reactor;Supercritical fluid is injected into the mixture to supercriticality, is gone forward side by side
Row intercalation obtains expansible graphite, and the pressure of the reaction is 4~20Mpa, and temperature is 5~45 DEG C, and the time is 0.2~
3h。
Further, the mass ratio of the graphite raw material, acid or acid anhydrides and oxidant is 1: 0.5~2: 0~0.5.
Further, the graphite raw material includes crystalline flake graphite, but not limited to this.
Further, the acid include sulfuric acid, nitric acid, phosphoric acid, perchloric acid, in acetic acid any one or it is two or more
The nitration mixture that acid is formed.
Further, the acid anhydrides includes acetic anhydride.
Further, the mass ratio of sulfuric acid and nitric acid is 2: 1 in the nitration mixture.
Further, the oxidant include in potassium permanganate, hydrogen peroxide, potassium bichromate, sodium dichromate, perchloric acid, bromic acid
Any one in sodium, but not limited to this.
Further, the supercritical fluid includes appointing in supercritical carbon dioxide, supercritical nitrogen, overcritical argon gas
Meaning is a kind of, but not limited to this.
Compared with prior art, the method that supercritical fluid auxiliary provided by the invention prepares expansible graphite is faced using super
Boundary's fluid prepares expansible graphite, effectively improves the utilization ratio of acid and oxidant as solvent, auxiliary intercalation, by acid and oxygen
The utilization ratio of agent promotes 3 times or more, and traditional handicraft acid and oxidant utilization ratio are less than 5% under same expansion multiplying power, originally
Utilization ratio can be promoted to 15% or more by the method that invention provides, and substantially reduce acid and oxidant in traditional processing technology
The dosage of acid and oxidant can be reduced about 70% by dosage under the conditions of same expansion multiplying power;Method provided by the invention can be with
It is a large amount of to save Material Cost, while reducing the generation and discharge of spent acid, more high-efficiency environment friendly.
Description of the drawings
Fig. 1 is the principle that a kind of supercritical fluid auxiliary prepares expansible graphite method in an of the invention exemplary embodiments
Structural schematic diagram.
Specific implementation mode
In view of deficiency in the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
An embodiment of the present invention provides a kind of methods that supercritical fluid auxiliary prepares expansible graphite comprising:
Mixture comprising graphite raw material and acid or acid anhydrides is placed in sealing reactor;
Supercritical fluid is injected into the mixture to supercriticality, and carries out intercalation, is obtained and be may expand stone
The pressure of ink, the reaction is 4~20Mpa, and temperature is 5~45 DEG C, and the time is 0.2~3h.
Further, the intercalation carries out under conditions of to hybrid reaction system prolonged agitation.
Further, the method further includes:After the intercalation, the pressure in reactor will be sealed
It is down to normal pressure, reaction product is washed to neutrality, most obtains expansible graphite after drying process afterwards.
Further, 50~80 DEG C of the temperature of the drying process, the time be 6~for 24 hours.
In some more specific embodiment, the method further includes:Will include graphite raw material, acid or acid anhydrides with
The mixture of oxidant is placed in sealing reactor;Supercritical fluid is injected into the mixture to supercriticality, is gone forward side by side
Row intercalation obtains expansible graphite, and the pressure of the reaction is 4~20Mpa, and temperature is 5~45 DEG C, and the time is 0.2~
3h。
Further, the mass ratio of the graphite raw material, acid or acid anhydrides and oxidant is 1: 0.5~2: 0~0.5.
Further, the graphite raw material includes crystalline flake graphite, but not limited to this.
Further, the acid include sulfuric acid, nitric acid, phosphoric acid, perchloric acid, in acetic acid any one or it is two or more
The nitration mixture that acid is formed.
Further, the acid anhydrides includes acetic anhydride.
Further, the mass ratio of sulfuric acid and nitric acid is 2: 1 in the nitration mixture.
Further, the oxidant include in potassium permanganate, hydrogen peroxide, potassium bichromate, sodium dichromate, perchloric acid, bromic acid
Any one in sodium, but not limited to this.
Further, the supercritical fluid includes appointing in supercritical carbon dioxide, supercritical nitrogen, overcritical argon gas
Meaning is a kind of, but not limited to this.
The technical solution, its implementation process and principle etc. will be further explained in conjunction with specific embodiments as follows
It is bright.
Referring to Fig. 1, a kind of method that supercritical fluid auxiliary prepares expansible graphite, including:
By the acid comprising 0.5~2 parts by weight or acid anhydrides, the oxidant of 0~0.5 parts by weight, 1 parts by weight crystalline flake graphite it is mixed
Object is closed to be added in sealing reactor;
Supercritical fluid is injected into the mixture, and 0.2~3h of intercalation is carried out under stirring condition;
After completion of the reaction, the pressure sealed in reactor is down to normal pressure, reacted product is washed to neutrality, at dry
Expansible graphite is obtained after reason.
Embodiment 1
A kind of method that supercritical fluid auxiliary prepares expansible graphite, may comprise steps of:
(1) by sulfuric acid and nitric acid in mass ratio 2: 1, it is configured to nitration mixture;
(2) by nitration mixture that step (1) prepares and potassium permanganate in mass ratio 1: 0.05 in being mixed in reactor to permanganic acid
Potassium is completely dissolved, and the crystalline flake graphite of 1 part of quality is added;
(3) it injects carbon dioxide into reactor, pressure 15MPa, 35 DEG C of temperature is set, until carbon dioxide is in supercritical state
State;
(4) it is stirred to react 0.5h;
(5) pressure in reactor is down to normal pressure by pressure release;
(6) reaction product is washed to neutrality, and dry complete in 60 DEG C, obtains expansible graphite.
Embodiment 2
Preparation method substantially with embodiment 1, the difference is that:The mass ratio of nitration mixture and potassium permanganate and crystalline flake graphite is
0.5:0.03:1。
Embodiment 3
Preparation method substantially with embodiment 1, the difference is that:The mass ratio of nitration mixture and potassium permanganate and crystalline flake graphite is
2:0.1:1。
Embodiment 4
Preparation method substantially with embodiment 1, the difference is that:Oxidant used is sodium dichromate.
Embodiment 5
Preparation method substantially with embodiment 1, the difference is that:Nitration mixture is configured by sulfuric acid and perchloric acid by 2: 1, nothing
Oxidant adds.
Comparative example
Traditional expansible graphite preparation process, method are as follows:
(1) by sulfuric acid and nitric acid in mass ratio 2: 1, it is configured to nitration mixture;
(2) nitration mixture that step 1 prepares is mixed with potassium permanganate in mass ratio 6: 0.15 to potassium permanganate and is completely dissolved, added
Enter the crystalline flake graphite of 1 part of quality;
(3) it is stirred to react 0.5h under the conditions of 25 DEG C.
(4) reactant is filtered, is washed to neutrality, 60 DEG C of dryings are complete, obtain expansible graphite.
The expansion multiplying power of embodiment 1-5 and the expansible graphite of comparative example acquisition, measurement result such as 1 institute of table are measured respectively
Show.Measurement method is as follows:By expansible graphite through 800 DEG C of high-temperature expansions of high temperature furnace, the worm volume mass ratio after expansion is measured.
The obtained expansible graphite expansion multiplying power of 1. Examples 1 to 5 of table, comparative example
Using supercritical fluid as solvent, auxiliary intercalation prepares expansible graphite, effectively carries method provided by the invention
The utilization ratio of acid and oxidant has been risen, the dosage of acid and oxidant in traditional processing technology is reduced;Under same expansion multiplying power,
The dosage of 67%~88% acid and oxidant can be reduced;Material Cost is substantial saved, while reducing the generation and discharge of spent acid,
More high-efficiency environment friendly.
It is verified by Experimental Comparison, the method that supercritical fluid auxiliary provided by the invention prepares expansible graphite utilizes super
For critical fluids as solvent, auxiliary intercalation prepares expansible graphite, effectively improves the utilization ratio of acid and oxidant, by acid and
The utilization ratio of oxidant promotes 3 times or more, under same expansion multiplying power traditional handicraft acid and oxidant utilization ratio less than 5%,
Utilization ratio can be promoted to 15% or more by method provided by the invention, substantially reduce acid and oxidant in traditional processing technology
Dosage, under the conditions of same expansion multiplying power can by acid and oxidant dosage reduce about 70%;Method provided by the invention can
Largely to save Material Cost, while reducing the generation and discharge of spent acid, more high-efficiency environment friendly.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
According to equivalent change or modification made by spirit of the invention, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of method that supercritical fluid auxiliary prepares expansible graphite, it is characterised in that including:
Mixture comprising graphite raw material and acid or acid anhydrides is placed in sealing reactor;
Supercritical fluid is injected into the mixture to supercriticality, and carries out intercalation, obtains expansible graphite, institute
The pressure for stating reaction is 4~20Mpa, and temperature is 5~45 DEG C, and the time is 0.2~3h.
2. according to the method described in claim 1, it is characterized in that:The intercalation is persistently stirred to hybrid reaction system
It is carried out under conditions of dynamic.
3. according to the method described in claim 1, characterized by further comprising:After the intercalation, it will seal
Pressure in reactor is down to normal pressure, and reaction product is washed to neutrality, most obtains expansible graphite after drying process afterwards;
And/or the temperature of the drying process be 50~80 DEG C, the time be 6~for 24 hours.
4. according to the method described in claim 1, characterized by further comprising:To include graphite raw material, acid or acid anhydrides and oxidation
The mixture of agent is placed in sealing reactor;Supercritical fluid is injected into the mixture to supercriticality, and is inserted
Layer reaction obtains expansible graphite, and the pressure of the reaction is 4~20Mpa, and temperature is 5~45 DEG C, and the time is 0.2~3h.
5. according to the method described in claim 4, it is characterized in that:The quality of the graphite raw material, acid or acid anhydrides and oxidant
The ratio between be 1: 0.5~2: 0~0.5.
6. according to the method described in claim 1 or 4 or 5, it is characterised in that:The graphite raw material includes crystalline flake graphite.
7. according to the method described in claim 1 or 4 or 5, it is characterised in that:The acid includes sulfuric acid, nitric acid, phosphoric acid, high chlorine
Any one in acid, acetic acid or the two or more sour nitration mixture formed;The acid anhydrides includes acetic anhydride.
8. according to the method described in claim 7, it is characterized in that:The mass ratio of sulfuric acid and nitric acid is 2: 1 in the nitration mixture.
9. method according to claim 4 or 5, it is characterised in that:The oxidant includes in potassium permanganate, hydrogen peroxide,
Any one in potassium bichromate, sodium dichromate, perchloric acid, sodium bromate.
10. method according to claim 1 or 4, it is characterised in that:The supercritical fluid includes overcritical titanium dioxide
Any one in carbon, supercritical nitrogen, overcritical argon gas.
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| CN201811001945.XA CN108689403A (en) | 2018-08-30 | 2018-08-30 | The method that supercritical fluid auxiliary prepares expansible graphite |
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| CN201811001945.XA CN108689403A (en) | 2018-08-30 | 2018-08-30 | The method that supercritical fluid auxiliary prepares expansible graphite |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668433A (en) * | 2019-11-25 | 2020-01-10 | 陕西师范大学 | Method for preparing graphite/graphene composite material by supercritical carbon dioxide fluid and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100298A (en) * | 2007-08-07 | 2008-01-09 | 哈尔滨工程大学 | Method for preparing expanded graphite |
| CN105129790A (en) * | 2015-10-10 | 2015-12-09 | 杭州海虹精细化工有限公司 | Novel method for preparing graphene oxide under supercritical water condition |
| CN105366668A (en) * | 2015-11-04 | 2016-03-02 | 福建翔丰华新能源材料有限公司 | Method for preparing graphene through supercritical fluid |
-
2018
- 2018-08-30 CN CN201811001945.XA patent/CN108689403A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100298A (en) * | 2007-08-07 | 2008-01-09 | 哈尔滨工程大学 | Method for preparing expanded graphite |
| CN105129790A (en) * | 2015-10-10 | 2015-12-09 | 杭州海虹精细化工有限公司 | Novel method for preparing graphene oxide under supercritical water condition |
| CN105366668A (en) * | 2015-11-04 | 2016-03-02 | 福建翔丰华新能源材料有限公司 | Method for preparing graphene through supercritical fluid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668433A (en) * | 2019-11-25 | 2020-01-10 | 陕西师范大学 | Method for preparing graphite/graphene composite material by supercritical carbon dioxide fluid and application |
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