CN107352530A - A kind of micro crystal graphite prepares graphene method - Google Patents
A kind of micro crystal graphite prepares graphene method Download PDFInfo
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- CN107352530A CN107352530A CN201710662243.5A CN201710662243A CN107352530A CN 107352530 A CN107352530 A CN 107352530A CN 201710662243 A CN201710662243 A CN 201710662243A CN 107352530 A CN107352530 A CN 107352530A
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- C01—INORGANIC CHEMISTRY
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- C01B2204/00—Structure or properties of graphene
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention belongs to technical field of material, more specifically, it is related to a kind of method that expanded graphite prepares graphene, the present invention is using micro crystal graphite as raw material, carry out first time chemical graft processing, the processing of first time high temperature puffing, second of intercalation processing, second of high temperature puffing processing successively to micro crystal graphite, obtain reexpansion micro crystal graphite, then reexpansion micro crystal graphite is ultrasonically treated twice, material must be peeled off, graphene is obtained to peeling off material progress press filtration, separation and cleaning.The inventive method is short as raw material, the technological process of production using micro crystal graphite, and cost is low, without sulphur, while can also prepare grapheme material in batches.
Description
Technical field
The invention belongs to technical field of material, more particularly to a kind of method that micro crystal graphite prepares graphene.
Background technology
Graphene is one kind by sp2The carbon atom of hydridization bonding in the form of hexagon grid, the two dimension of the carbon formed
Planar monolayer structure, it is the allotrope of carbon.Graphene is the elementary cell for building other dimension carbon materials, when it is with bag
When the mode wrapped up in, wind and piled up changes, the fullerene, one-dimensional CNT and three-dimensional stone of zero dimension can be formed respectively
Ink.Graphene has good electricity-optics performance, mechanical property, heat-conductive characteristic and the migration of high electric charge carrier
Rate, while also outstanding mechanical strength and pliability.These properties of graphene, it is allowed to be rapidly become by numerous concerns
The focus of research.The graphene and its derivative handled by chemical modification is even more the material with specific function, available for crystalline substance
Body pipe, liquid-crystal apparatus, electrochemica biological sensor, ultracapacitor, fuel cell, solar cell etc..Ground past
During studying carefully, people generally prepare graphite with mechanical stripping method, chemical vapour deposition technique, epitaxial growth method, oxidation-reduction method etc.
Alkene.
Meanwhile graphene is substantially and is prepared with crystalline flake graphite, native graphite has crystalloid (flakey) graphite and micro-
Brilliant (earthy) graphite, micro crystal graphite crystal diameter are typically smaller than 1 μm, and in crystallite aggregate, sorting is poor, therefore industrially not
As crystalline flake graphite is widely used.China's micro crystal graphite aboundresources, mainly contains in Hebei China, Hunan, Inner Mongol, Shanxi and Ji
The ground such as woods, account for global storage capacity more than half.Micro crystal graphite crystal is tiny, and aggregate is in earthy, without obvious crystalline orientation,
The industrial circles such as electronics, machinery, steel, casting, daily-use chemical industry tool has been widely used.
Micro crystal graphite compares with Scaly graphite, and crystal habit has prominent otherness, and the former is in inlay aggregate,
Small, the visible morphon under electron microscope of grain；The latter disperses flakey in monocrystalline, and chip naked eyes are visible.The two is in chemistry
Reactive nature, crystalline orientation etc. have notable difference.At present, native graphite is used to prepare expanded graphite material for raw material
Raw material used in the technology of material is generally crystalloid flaky graphite.Thus, use is never captured using traditional handicraft
Micro crystal graphite prepares the technical method of expansion micro crystal graphite.Also it is few on preparing expanded graphite material by raw material of micro crystal graphite
The research report of material or graphene technical method.
China's micro crystal graphite reserves are up to 2,000,000,000 tons, it would therefore be highly desirable to develop a kind of easy and effective and can be with micro crystal graphite
The method that batch prepares high-quality graphene powder.It is mostly crystalline flake graphite that it is raw materials used, which to prepare graphene method in batches, at present,
But the R and D to micro crystal graphite are extremely limited, generally with material outlet.With the exhaustive exploitation of the high-quality graphite in China,
It is extremely urgent to research and develop micro crystal graphite.
The content of the invention
For reasonable, abundant exploitation micro crystal graphite resource, the technical bottleneck that micro crystal graphite prepares grapheme material is broken through, micro-
On the basis of spar ink mineralogy attributes research, the technical method of the present invention is captured, its object is to provide one kind with microlite
Ink is short for raw material, the technological process of production, and cost is low, without sulphur, the method that grapheme material is prepared.
The purpose of the present invention is achieved by the following technical programs：
A kind of method that micro crystal graphite prepares graphene, it is characterised in that be using micro crystal graphite as raw material, to micro crystal graphite
First time chemical graft processing, the processing of first time high temperature puffing are carried out successively, at second of intercalation processing, second of high temperature puffing
Reason, obtains reexpansion micro crystal graphite, then reexpansion micro crystal graphite is ultrasonically treated twice, obtain stripping material, right
Peel off material progress press filtration, separation and cleaning and obtain graphene.
Preferably, the micro crystal graphite is Chenzhou City Shandong pool graphite powder, and its carbon content is 70~80%.
Preferably, the method that the micro crystal graphite prepares graphene, comprises the following steps：
S1. micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300~400 mesh, to micro crystal graphite are taken
Powder carries out first time intercalation processing, the processing of first time high temperature puffing, second of intercalation processing, second of expanding treatment successively, obtains
Reexpansion micro crystal graphite；
S2. reexpansion micro crystal graphite obtained by step S1 is placed in prestripping supersonic reaction device and reacted, obtained pre-
Peel off material；
S3. prestripping material in step S2 is mixed with stripper, be placed on after dilution in twice ultrasonic reaction unit anti-
Should, obtain peeling off material；
S4. material press filtration, separation will be peeled off in step S3, then collects Graphite Cake, stripper can then recycle；
S5. clean：Graphite Cake in step S4 is cleaned, obtains graphene；
Wherein, in step S2 the temperature of prestripping supersonic reaction device be 30~50 DEG C, frequency be 10000~25000Hz,
Flow velocity is 1.0~4.0m3/ h, circulation stirring speed are 1000~2000r/min, the ultrasonic disperse time is 0.5~2.0h；
The temperature of twice ultrasonic reaction unit is 30~50 DEG C in step S3, frequency is 18000~25000Hz, flow velocity is
2.0~5.0m3/ h, circulation stirring speed are 1000~2000r/min, the ultrasonic disperse time is 2~5h.
It is further preferred that step S1 comprises the following steps：
S11. micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300~400 mesh are taken；
S12. the potassium permanganate pure with the perchloric acid and chemistry of mass fraction 70% of microlite ink powder obtained by step S1 is put
In carrying out first time chemical graft processing in reaction unit, inflatable micro crystal graphite acidic suspension is obtained, gained may expand
Micro crystal graphite acidic suspension filters, and reservation filtrate is standby, then washs filtrate, dries, and obtains once inflatable micro-
Spar ink；
S13. micro crystal graphite will be once may expand obtained by step S2 to be placed in graphite expansion stove, and first is carried out at 800 DEG C
Secondary high-temperature expansion, is once expanded micro crystal graphite；
S14. it is raw material to take obtained by appropriate step S3 once expansion micro crystal graphite, concentrated nitric acid and change with mass fraction 65%
Learn pure potassium permanganate and be placed in second of chemical graft processing of progress in reaction unit, obtain the acid suspension of inflatable micro crystal graphite
Liquid, the filtering of micro crystal graphite acidic suspension, washing are may expand to gained, is dried, obtains secondary inflatable micro crystal graphite；
S15. secondary inflatable micro crystal graphite obtained by step S4 is placed in graphite expansion stove, second is carried out at 900 DEG C
Secondary high-temperature expansion, obtain reexpansion micro crystal graphite；
Wherein：It is 30 μm that filter membrane maximum diameter of hole used is filtered described in step S2 and S4；The washing refers to crossing filter residue
With 10% salt acid elution 3~5 times, then it is washed with deionized to 7 or so；The drying refers to be dried under the conditions of 60~80 DEG C
2h。
It is further preferred that first time chemical graft step includes described in step S12：
S121. it is 10~30 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；
S122. it is 1 by the mass ratio of the micro crystal graphite powder and potassium permanganate：2~8 add potassium permanganate, in room temperature
Under stir after, be warming up to 30~60 DEG C and continue stirring reaction 1~3.0h；
S123. adding deionized water makes the temperature in the reaction unit be increased to 60~100 DEG C, is further continued for stirring reaction
1~3.0h.
Comprise the following steps it is further preferred that step S13 carries out first time high-temperature expansion in graphite expansion stove：
S131. feed：Using conserving graphite expanding furnace, an expansible graphite is put into burner hearth by charging aperture, it is described
The temperature of charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；
S132. expand：The expansion temperature of burner hearth is 800 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S133. discharge：After completing step S132, discharging opening temperature is 50 DEG C, then collects to obtain once in discharge outlet
Expanded graphite.
It is further preferred that second of chemical graft step includes described in step S14：
S141. will once expand micro crystal graphite obtained by step S3 to mix with nitric acid, nitric acid is by with once expanding micro crystal graphite
It is 1~10 by liquid-solid ratio：1L/Kg is mixed evenly；
S142. mixed liquor obtained by S141 is mixed with gained filtrate after step S2 filterings and be placed in reaction unit,
After stirring at room temperature, it is warming up to 30~60 DEG C and continues 1~3.0h of stirring reaction；
S143. deionized water is added, the temperature in the reaction unit is increased to 60~100 DEG C, it is anti-to be further continued for stirring
Answer 1~3.0h.
Comprise the following steps it is further preferred that step S15 carries out second of high-temperature expansion in graphite expansion stove：
S151. feed：Using conserving graphite expanding furnace, expansible graphite is put into burner hearth by charging aperture, the charging
The temperature of mouth is 30 DEG C, and dispensing speed is 2Kg/h；
S152. expand：The expansion temperature of burner hearth is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S153. discharge：After completing step S152, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet secondary
Expanded graphite.
Graphene is prepared in the method that the present invention prepares graphene always according to micro crystal graphite.
Meanwhile the present invention provides the production system that a kind of batch prepares the method for graphene, including obtain secondary inflatable
Processing system after graphite, specifically includes conserving graphite expanding furnace, twice ultrasonic device and filter, conserving graphite expanding furnace with it is secondary
Vltrasonic device is connected, and twice ultrasonic device is connected with filter；
Conserving graphite expanding furnace includes body of heater, feeding device, drawing mechanism and control device, and expansible graphite passes through feeding device
To body of heater, then collected by drawing mechanism；Drawing mechanism is located above body of heater, and feeding device is located at below body of heater；In body of heater
Provided with heater, body of heater inner bottom part is additionally provided with air-flow shower nozzle, and air-flow shower nozzle also includes source of the gas, airflow line and gas flow optimized
Valve, source of the gas connection airflow line, airflow line connection air-flow shower nozzle, control damper is located in airflow line, on air-flow shower nozzle
Side is provided with feeding device, specifically includes processor and controller using feed screw, control device, processor is provided with chain of command
Plate is simultaneously connected with controller, and controller includes the first controller, second controller and the 3rd controller, the first controller and air-flow
The control damper connection of shower nozzle, second controller are connected with feeding device, and the 3rd controller is connected with heater；Discharging dress
Put and cooling device is additionally provided between body of heater, cooling device includes heat exchanger tube and water cooling tube, and one end of heat exchanger tube connects body of heater, separately
One end connects drawing mechanism, and heat exchanger tube and horizontal angle are 45 DEG C~90 DEG C, and water cooling tube is arranged in heat exchanger tube in the shape of a spiral
On；Drawing mechanism includes multiple reserves storehouses and connecting pipe, and connecting pipe one end is connected with heat exchanger tube, and is provided with cyclonic separation
Device, the other end are connected with exhaust outlet, and multiple subtubes are additionally provided with connecting pipe and are connected respectively with reserves storehouse；Connecting pipe and water
The angle of horizontal line is 45 DEG C~90 DEG C；Agitator is additionally provided with body of heater, agitator is spiral agitator, passes through motor and ball
Leading screw coordinates so that agitator does upper and lower linear motion in body of heater, so as to drive the airflow reflux in body of heater；The charging
Heater is provided with device；
Twice ultrasonic device includes prestripping device and ultrasonic stripping off device, and prestripping device includes the first batch mixing pond and more
The first circulation system of individual first ultrasonic reaction kettle composition, the first ultrasonic reaction kettle include Vltrasonic device and reactor, and first is mixed
Material pond is provided with the dog-house being connected with graphite expansion, and upper end is connected by the first reflux line with the first ultrasonic reaction kettle, under
End connects the first ultrasonic reaction kettle by the first ultrasonic reaction kettle pipeline respectively, the first connecting pipe is connected with the first discharge port,
First ultrasonic reaction kettle pipeline is provided with centrifugal pump and flowmeter, and multiple first ultrasonic reaction kettles connect in difference in height arrangement, its
Connected between middle horizontal level minimum the first ultrasonic reaction kettle and the first connecting pipe by the first drainage conduit；
The second circulation system that ultrasonic stripping off device includes the second batch mixing pond and multiple second ultrasonic reaction kettles form, second
Ultrasonic reaction kettle includes Vltrasonic device and reactor, and the upper end in the second batch mixing pond passes through the second reflux line and the second ultrasonic reaction
Kettle is connected, and lower end is connected with the second connecting tube；Second connecting tube be provided be connected with the first discharge port charging aperture, centrifugal pump,
Flowmeter and the second discharge port being connected with filter, the second ultrasonic reaction kettle horizontal level are sequentially connected, and provided with exhaust
Valve, and be connected by the second drainage conduit with the second connecting tube；
Filter is plate and frame type filter-press.
Compared with the prior art, the beneficial effects of the present invention are：
(1) present invention prepares expanded graphite alkene material using micro crystal graphite, there is provided a kind of new application of micro crystal graphite.
(2) present invention using micro crystal graphite prepares creative use during grapheme material intercalation combines two twice
Secondary high-temperature expansion prepares reexpansion micro crystal graphite, the expansion multiple of reexpansion micro crystal graphite is up to 300 times, more has
Beneficial to subsequently preparing grapheme material.The present invention is added without the material of sulfur-bearing during preparing grapheme material, therefore in height
During temperature prepares expansion micro crystal graphite, sulfur dioxide pollution thing, the expanded graphite product and graphene material of preparation are not produced
Material also not sulfur-bearing, improves the corrosion resistance of grapheme material, the present invention is in high-temperature expansion processing procedure, by traditional high temperature
Plavini and graphite expansion stove combine, using optimal expansion temperature, and around expansion temperature by joining to raw material and technique
Several control can effectively improve the stability of product, so as to prepare the controllable expanded graphite of expansion multiple, i.e., in expansion multiple
200~300 distributive law highest, the raw material of graphene is prepared as mechanical stripping method using above-mentioned expanded graphite, can be very big
Improve the stripping rate of graphene.It is more beneficial for the process of subsequent ultrasonic stripping.
(3) further scientific and reasonable setting intercalation processing temperature and the high-temperature expansion temperature twice twice of the present invention, guarantee
The intercalation effect and expansion multiple of micro crystal graphite, while original micro crystal graphite structure is also remained to greatest extent.
(4) present invention uses micro crystal graphite, and the chip of micro crystal graphite is less than crystalline flake graphite, is produced by raw material of micro crystal graphite
Graphene will not only be greatly lowered the cost of graphene, while will also make up market to small size, specific area graphene
Demand, solve in the prior art the features such as graphene preparation method cycle is long, is difficult to meet industrialized production, also utilize simultaneously
The micro crystal graphite resources advantage of China's abundant,
(5) present invention is on the basis of tradition machinery stripping method prepares graphene, around the expansible graphite as former
Material, prepares graphene technique, graphene quantum dot is stripper, is increased in prior art basis by optimizing mechanical stripping method
Prestripping handling process, coordinate twice ultrasonic processing, and optimize the technological parameter of supersound process, realize the mass of graphene
Production, the graphene can be applied to prepare graphene powder by processing further.
(6) present invention forms temperature range, reason is graphite in itself to charging aperture, the restriction of the temperature of discharging opening
Belong to the material of the cold property of heat；And by setting rate of feeding, wind speed to realize separation to control puffing time, then by wind speed
Collect, realize extensive preparation, and without inert gas shielding, you can prevent expansion temperature is too high from can make graphite high temperature oxygen
Change, so as to reduce the swelling volume of graphite.Currently preferred graphite expansion stove adds agitator in body of heater so that in body of heater
Air-flow form convection current, ensure that being heated evenly for intercalated graphite, avoid inboard wall of furnace body and center section temperature it is different so as to
The problem of causing uneven heating even, reaction efficiency is greatly improved.Currently preferred graphite expansion stove is put using two floors
Put, the processing sequence according to raw material is that from the bottom up, heat exchanger tube and connecting pipe have certain angle with horizontal line, pass through weight
The cooperation of power and wind speed, that is, solve expanded graphite and get stuck problem, improve reaction yield, while also solve compared to being disposed vertically
Space.
Brief description of the drawings
Fig. 1 is the production system schematic diagram of graphene of the present invention.
Fig. 2 is graphite expansion furnace structure figure of the present invention.
Fig. 3 is prestripping device schematic device of the present invention.
Fig. 4 is the ultrasonic stripping off device schematic diagram of the present invention.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Embodiment 1
The method that the present invention prepares expansion microcrystalline graphite material with micro crystal graphite, including step are as follows：Including graphite expansion
Stove, using high-temperature expansion method, comprise the following steps：
S1. micro crystal graphite raw material, phosphorus content 70%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh are taken；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in progress first time in reaction unit
Intercalation processing is learned, obtains inflatable micro crystal graphite acidic suspension, the filtering of micro crystal graphite acidic suspension is may expand to gained, is protected
Reserved filtrate is standby, then washs filtrate, dries, obtains and once may expand micro crystal graphite；Wherein, first time chemical graft
Concretely comprise the following steps：S21. it is 10 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S22. press
The mass ratio of micro crystal graphite powder and strong oxidizer is 2：1 adds strong oxidizer, after being stirred at room temperature uniformly, is warming up to 30 DEG C
Continue stirring reaction 3h；S23. adding deionized water makes the temperature in reaction unit be increased to 60 DEG C, is further continued for stirring reaction 3h；
S3. micro crystal graphite will be once may expand obtained by step S2 to be placed in graphite expansion stove, carries out first time high-temperature expansion,
Once expanded micro crystal graphite；Wherein first time high-temperature expansion concretely comprises the following steps：S31. feed：Using conserving graphite expanding furnace,
Expansible graphite is put into burner hearth by charging aperture, the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；
S32. expand：The expansion temperature of burner hearth is 800 DEG C, by controlled wind speed come to control Bulking Time be 5s；S33. discharge：Complete step
After rapid S32, discharging opening temperature is 50 DEG C, then collects to obtain an expanded graphite in discharge outlet；
S4. will once expand micro crystal graphite obtained by step S3 to mix with nitric acid, gained filtrate after then filtering with step S2
It is mixed to be placed in reaction unit and is reacted, obtains inflatable micro crystal graphite acidic suspension, crystallite may expand to gained
The filtering of graphite acidic suspension, washing, dry, obtain secondary inflatable micro crystal graphite；Wherein, the specific step of second of chemical graft
Suddenly it is：S41. an expanded graphite obtained by step S3 is mixed with nitric acid, nitric acid amount is according to the liquid with once expanding micro crystal graphite
Gu than being 1：1L/Kg is added；S42. gained filtrate after step S2 is filtered is added, 60 DEG C is warming up to and continues stirring reaction 1h；S43.
Adding deionized water makes the temperature in reaction unit be increased to 100 DEG C, is further continued for stirring reaction 1h；
S5. secondary inflatable micro crystal graphite obtained by step S4 is placed in graphite expansion stove, carries out second of high-temperature expansion,
Obtain reexpansion graphite；Wherein first time high-temperature expansion concretely comprises the following steps：S51. feed：, can using conserving graphite expanding furnace
Expanded graphite is put into burner hearth by charging aperture, and the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；S52. it is swollen
It is swollen：The expansion temperature of burner hearth is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；S53. discharge：Complete step S52
Afterwards, discharging opening temperature is 50 DEG C, then collects to obtain reexpansion graphite in discharge outlet.
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 150, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 200m2/ g,.
The expansion multiple of reexpansion micro crystal graphite obtained by the present embodiment is 210, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 302m2/ g, resistivity are 9.78 × 10-4Ω·m。
Embodiment 2
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 70%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 15 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：
1L/Kg is mixed evenly；S22. it is 4 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, in room
After being stirred under temperature, it is warming up to 40 DEG C and continues stirring reaction 2h；S23. addition deionized water makes the temperature liter in reaction unit
Up to 70 DEG C, it is further continued for stirring reaction 2h；
S4. second chemical graft concretely comprises the following steps：S41. micro crystal graphite and nitric acid will be once expanded obtained by step S3
Mixing, nitric acid amount are 1 according to once expanding micro crystal graphite liquid-solid ratio：1L/Kg is added；S42. add obtained by after step S2 filterings
Filtrate, it is warming up to 60 DEG C and continues stirring reaction 2h；S43. adding deionized water makes the temperature in reaction unit be increased to 90 DEG C, then
Continue stirring reaction 2h；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 180, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 302m2/g。
The expansion multiple of reexpansion micro crystal graphite obtained by the present embodiment is 231, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 460m2/ g, resistivity are 8.34 × 10-4Ω·m。
Embodiment 3
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 75%, crushing and grinding, to the microlite ink powder that granularity is 350 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 20 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：
1L/Kg is mixed evenly；S22. it is 6 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, in room
After being stirred under temperature, it is warming up to 50 DEG C and continues stirring reaction 2h；S23. addition deionized water makes the temperature liter in reaction unit
Up to 80 DEG C, it is further continued for stirring reaction 2h；
S4. second chemical graft concretely comprises the following steps：S41. micro crystal graphite and nitric acid will be once expanded obtained by step S3
Mixing, nitric acid amount are 1 according to once expanding micro crystal graphite liquid-solid ratio：1L/Kg is added；S42. add obtained by after step S2 filterings
Filtrate, it is warming up to 50 DEG C and continues stirring reaction 2h；S43. adding deionized water makes the temperature in reaction unit be increased to 80 DEG C, then
Continue stirring reaction 2h；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 160, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 410m2/g。
The expansion multiple of reexpansion micro crystal graphite obtained by the present embodiment is 246, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 540m2/ g, resistivity are 9.34 × 10-4Ω·m。
Embodiment 4
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 75%, crushing and grinding, to the microlite ink powder that granularity is 350 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 20 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：
1L/Kg is mixed evenly；S22. it is 6 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, in room
After being stirred under temperature, it is warming up to 50 DEG C and continues stirring reaction 1h；S23. addition deionized water makes the temperature liter in reaction unit
Up to 90 DEG C, it is further continued for stirring reaction 1h；
S4. second chemical graft concretely comprises the following steps：S41. micro crystal graphite and nitric acid will be once expanded obtained by step S3
Mixing, nitric acid amount are 5 according to once expanding micro crystal graphite liquid-solid ratio：1L/Kg is added；S42. add obtained by after step S2 filterings
Filtrate, it is warming up to 60 DEG C and continues stirring reaction 1h；S43. adding deionized water makes the temperature in reaction unit be increased to 100 DEG C,
It is further continued for stirring reaction 1h；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 198, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 393m2/g。
The expansion multiple of reexpansion micro crystal graphite obtained by the present embodiment is 300, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 590m2/ g, resistivity are 8.99 × 10-4Ω·m。
Embodiment 5
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 80%, crushing and grinding, to the microlite ink powder that granularity is 350 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 25 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：
1L/Kg is mixed evenly；S22. it is 7 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, in room
After being stirred under temperature, it is warming up to 60 DEG C and continues stirring reaction 1h；S23. addition deionized water makes the temperature liter in reaction unit
Up to 100 DEG C, it is further continued for stirring reaction 1h；
S4. second chemical graft concretely comprises the following steps：S41. micro crystal graphite and nitric acid will be once expanded obtained by step S3
Mixing, nitric acid amount are 5 according to once expanding micro crystal graphite liquid-solid ratio：1L/Kg is added；S42. add obtained by after step S2 filterings
Filtrate, it is warming up to 30 DEG C and continues stirring reaction 3h；S43. adding deionized water makes the temperature in reaction unit be increased to 60 DEG C, then
Continue stirring reaction 3h；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 201, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 200m2/g。
The expansion multiple of reexpansion micro crystal graphite obtained by the present embodiment is 289, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 588m2/ g, resistivity are 9.21 × 10-4Ω·m。
Embodiment 6
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 80%, crushing and grinding, to the microlite ink powder that granularity is 400 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 30 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：
1L/Kg is mixed evenly；S22. it is 8 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, in room
After being stirred under temperature, it is warming up to 50 DEG C and continues stirring reaction 1h；S23. addition deionized water makes the temperature liter in reaction unit
Up to 80 DEG C, it is further continued for stirring reaction 1h；
S4. second chemical graft concretely comprises the following steps：S41. micro crystal graphite and nitric acid will be once expanded obtained by step S3
Mixing, nitric acid amount are 10 according to once expanding micro crystal graphite liquid-solid ratio：1L/Kg is added；S42. institute after step S2 is filtered is added
Filtrate is obtained, 60 DEG C is warming up to and continues stirring reaction 2h；S43. adding deionized water makes the temperature in reaction unit be increased to 90 DEG C,
It is further continued for stirring reaction 2h；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 170, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 310m2/ g, resistivity are 1 × 10-5~1 × 10-2Ω·m。
The expansion multiple of reexpansion micro crystal graphite obtained by the present embodiment is 280, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 520m2/ g, resistivity are 1 × 10-5~1 × 10-2Ω·m。
Embodiment 7
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material, phosphorus content 80%, crushing and grinding, to the microlite ink powder that granularity is 400 mesh are taken；
S2. first time chemical graft concretely comprises the following steps：S21. it is 30 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：
1L/Kg is mixed evenly；S22. it is 8 by the mass ratio of micro crystal graphite powder and potassium permanganate：1 adds potassium permanganate, in room
After being stirred under temperature, it is warming up to 50 DEG C and continues stirring reaction 2h；S23. addition deionized water makes the temperature liter in reaction unit
Up to 80 DEG C, it is further continued for stirring reaction 2h；
S4. second chemical graft concretely comprises the following steps：S41. micro crystal graphite and nitric acid will be once expanded obtained by step S3
Mixing, nitric acid amount are 1 according to once expanding micro crystal graphite liquid-solid ratio：1L/Kg is added；S42. add obtained by after step S2 filterings
Filtrate, it is warming up to 60 DEG C and continues stirring reaction 1h；S43. adding deionized water makes the temperature in reaction unit be increased to 90 DEG C, then
Continue stirring reaction 1h；
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 169, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 330m2/g。
The expansion multiple of reexpansion micro crystal graphite obtained by the present embodiment is 279, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 549m2/ g, resistivity are 9.09 × 10-4Ω·m。
Embodiment 8
Referring to Fig. 1~4, the present embodiment provides the production system that a kind of batch prepares the method for graphene, including obtains two
Processing system after secondary expansible graphite, specifically include conserving graphite expanding furnace 101, twice ultrasonic device and filter 104, stone
Black puffing furnace 101 is connected with twice ultrasonic device, and twice ultrasonic device is connected with filter 104；
Graphite expansion stove includes body of heater 1, feeding device 2, drawing mechanism 3 and control device, raw material by feeding device 2 to
Body of heater 1, then collected by drawing mechanism 3；Drawing mechanism 3 is located above body of heater, and feeding device 2 is located at below body of heater；Body of heater 1
Interior to be provided with heater 11, the present embodiment uses Resistant heating, and the inner bottom part of body of heater 1 is additionally provided with air-flow shower nozzle 4, air-flow shower nozzle 4
Also include source of the gas 41, airflow line 42 and control damper 43, source of the gas 41 is air, and connects airflow line 42, airflow line
42 connection air-flow shower nozzles 4, control damper 43 is located in airflow line 42, and the top of air-flow shower nozzle 4 is provided with feeding device 2, specifically
Using feed screw, control device includes processor 5 and controller, and processor 5 is provided with control panel and is connected with controller,
Controller includes the first controller 53, the controller 51 of second controller 52 and the 3rd, the gas of the first controller 53 and air-flow shower nozzle 4
Flow control valve 43 is connected, and second controller 52 is connected with feeding device 2, and the 3rd controller 51 is connected with heater 11；Wherein,
Processor 5 uses microprocessor, and the first controller uses air inlet valve-driving circuit, and second controller is using charging electrohydraulic valve actuator
Road, the 3rd controller use heat driven circuit.Cooling device 7 is additionally provided between drawing mechanism 3 and body of heater 1, cooling device 7 wraps
Include heat exchanger tube 71 and water cooling tube 72, one end connection body of heater 1 of heat exchanger tube 71, other end connection drawing mechanism 3, heat exchanger tube 71 and water
The angle of horizontal line is 45 DEG C~90 DEG C, and water cooling tube 72 is arranged on heat exchanger tube 71 in the shape of a spiral；Drawing mechanism 3 includes multiple reserves
Storehouse 31 and connecting pipe 32, the one end of connecting pipe 32 are connected with heat exchanger tube 71, and are provided with cyclone separator 33, the other end and exhaust
Mouth 34 connects, and be additionally provided with multiple subtubes 35 on connecting pipe 32 is connected with reserves storehouse 31 respectively；Connecting pipe and 32 horizontal lines
Angle be 45 DEG C~90 DEG C.Wherein, processor uses microprocessor, and the first controller uses air inlet valve-driving circuit, and second
Controller uses heat driven circuit using charging valve-driving circuit, the 3rd controller.Agitator 8 is additionally provided with body of heater 1, is stirred
Device 8 is spiral agitator, is coordinated by motor and ball-screw so that agitator 8 does upper and lower straight line fortune in body of heater 1
It is dynamic, so as to drive the airflow reflux in body of heater 1.
Twice ultrasonic device includes prestripping device 102 and ultrasonic stripping off device 103, and prestripping device 102 includes first
Batch mixing pond 96 and the first circulation system of multiple first ultrasonic reaction kettles composition, the first ultrasonic reaction kettle include the He of Vltrasonic device 12
Reactor 26, the first batch mixing pond 96 are provided with the dog-house 91 being connected with graphite expansion 101, and upper end passes through the first reflux line 10
It is connected with the first ultrasonic reaction kettle, lower end connects the first ultrasonic reaction kettle, first by the first ultrasonic reaction kettle pipeline 13 respectively
Connecting pipe 14 is connected with the first discharge port 20, and the first ultrasonic reaction kettle pipeline 13 is provided with centrifugal pump 22 and flowmeter 21, more
Individual first ultrasonic reaction kettle is in difference in height arrangement connection, wherein the first minimum ultrasonic reaction kettle of horizontal level and the first connecting tube
Connected between road 14 by the first drainage conduit 15；
The second circulation system that ultrasonic stripping off device 103 includes the second batch mixing pond 23 and multiple second ultrasonic reaction kettles form
System, the second ultrasonic reaction kettle include Vltrasonic device 27 and reactor 26, and the upper end in the second batch mixing pond passes through the second reflux line 25
It is connected with the second ultrasonic reaction kettle, lower end is connected with the second connecting tube 28；Second connecting tube 28 is provided with and the first discharge port 20
Charging aperture 94, centrifugal pump 91, flowmeter 92 and the second discharge port 29 being connected with filter 104 of connection, the second ultrasound are anti-
Answer kettle horizontal level to be sequentially connected, and be provided with air bleeding valve, and be connected by the second drainage conduit 30 with the second connecting tube 28；
Filter 104 is plate and frame type filter-press.
The present embodiment operation principle is as follows：
1. using the graphite after intercalation as raw material, entered by feed arrangement 2 in body of heater 1, in the effect of air-flow shower nozzle 4
Under, completion is expanded, and is blown out to cooling device 7, obtains expanded graphite, is then collected by reserves storehouse 31, is then transported pre-
Stripping off device；Expanded time and temperature can be controlled by control panel, specifically processor is by controlling the first controller
Air velocity and charging rate are controlled with second controller, so as to control intercalated graphite expanded reaction time, the 3rd control
Device can control the temperature of heater 11, realize the intelligentized control method technological parameter of graphite expansion control；
2. expanded graphite and stripper are added in the first batch mixing pond 96, stirred by motor, then open ball valve 19,
Centrifugal pump 22 is opened, carries out multiple circular response, after having reacted, centrifugal pump 22 is closed, opens ball valve 16, the and of ball valve 18 successively
Ball valve 17, the expanded graphite for completing prestripping enter ultrasonic stripping off device by the first discharge port 20；
3. the expanded graphite that prestripping is completed in step S2 enters the second connecting tube 28 by charging aperture 94, ball is now opened
Valve 94, ball valve 36, ball valve 37 is closed, open centrifugal pump 91, carry out multiple circulating ultrasonic glass reaction, stone is obtained after having reacted
Black alkene slurry, centrifugal pump 91 is closed, open ball valve 30, ball valve 37 successively, now graphene slurry is entered by the second discharge port 29
Enter plate and frame type filter-press；
4. the graphene slurry that plate and frame type filter-press is completed to reaction filters, collection obtains product.
The present embodiment controls the temperature of discharging opening by cooling device, and heater 6 also is provided with charging aperture
To control the temperature of charging aperture, specific the present embodiment can be added using resistance wire 61 to the discharge pipe in feeding device
Heat.
The present embodiment can control time and the temperature of expansion by control panel, and specifically processor passes through control first
Controller and second controller control air velocity and charging rate, so as to controlling the reaction time that intercalated graphite expands, the
Three controllers can control the temperature of heater, realize the intellectuality of graphite expansion, reach and be precisely controlled.
The present embodiment graphite expansion stove is placed using two floors, and the processing sequence according to raw material is heat exchange from the bottom up
Pipe and connecting pipe and horizontal line have certain angle, by the cooperation of gravity and wind speed, that is, solve expanded graphite and get stuck and ask
Topic, reaction yield is improved, while also solve space compared to being disposed vertically.
The present embodiment graphite expansion stove adds agitator 8 in body of heater 1 so that the air-flow in body of heater 1 forms convection current, ensures
Being heated evenly for intercalated graphite, so that the expanded reaction efficiency of intercalated graphite be significantly increased.
The present embodiment combines puffing furnace and twice ultrasonic device, and the expanded stone of high magnification numbe is prepared by puffing furnace
Ink, then carry out prestripping as raw material and ultrasound is peeled off, carry out circular response, coordinating twice ultrasonic to peel off can be greatly improved
Charge stripping efficiency, it is achieved thereby that graphene is extensive, the production of high efficiency, low cost.
Comparative example 1
Comparative example 1 is with the difference of embodiment 1：First time high-temperature expansion and second of high-temperature expansion are swollen without using high temperature
Swollen stove, using traditional Muffle furnace, coordinate high-temperature expansion method, specifically different steps is as follows：
S3. micro crystal graphite will be once may expand obtained by step S2 it is placed in Muffle furnace and heat calcination process, enters at 800 DEG C
Row first time high-temperature expansion, Bulking Time 30s, is once expanded micro crystal graphite；
S5. secondary inflatable micro crystal graphite obtained by step S4 is placed in Muffle furnace and heats calcination process, entered at 900 DEG C
Second of high-temperature expansion of row, Bulking Time 30s, obtains reexpansion micro crystal graphite.
The expansion multiple that micro crystal graphite is once expanded obtained by the present embodiment is 122, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 296m2/g。
The expansion multiple of reexpansion micro crystal graphite obtained by the present embodiment is 190, is wormlike porous material, pore-size distribution
Scope is 1~100nm, specific surface area 510m2/ g, resistivity are 2.08 × 10-4Ω·m。
Embodiment 9
The present embodiment provides a kind of preparation method of graphene, comprises the following steps：
S1. the expansion micro crystal graphite being prepared using embodiment 4 is as raw material；
S2. expansion micro crystal graphite obtained by step S1 is placed in prestripping supersonic reaction device and reacted, obtain prestripping
Material；
S3. prestripping material in step S2 is mixed with graphene quantum dot, twice ultrasonic reaction is placed on after 5 times of dilution
Reacted in device, obtain peeling off material；
S4. material press filtration, separation will be peeled off in step S3, then collects Graphite Cake, stripper can then recycle；
S5. clean：Graphite Cake in step S4 is washed with deionized 5 times, obtains graphene；
Wherein, in step S2 the temperature of prestripping supersonic reaction device be 30 DEG C, frequency 10000Hz, flow velocity be
1.0m3/ h, circulation stirring speed are 1000r/min, the ultrasonic disperse time is 2.0h；
In step S3 the temperature of twice ultrasonic reaction unit be 50 DEG C, frequency 25000Hz, flow velocity 2.0m3/ h, circulation
Mixing speed is 1000r/min, the ultrasonic disperse time is 5.0h.
Embodiment 10
The present embodiment provides a kind of preparation method of graphene, comprises the following steps：
S1. the expansion micro crystal graphite being prepared using embodiment 4 is as raw material；
S2. expansion micro crystal graphite obtained by step S1 is placed in prestripping supersonic reaction device and reacted, obtain prestripping
Material；
S3. prestripping material in step S2 is mixed with graphene quantum dot, twice ultrasonic reaction is placed on after 5 times of dilution
Reacted in device, obtain peeling off material；
S4. material press filtration, separation will be peeled off in step S3, then collects Graphite Cake, stripper can then recycle；
S5. clean：Graphite Cake in step S4 is washed with deionized 5 times, obtains graphene；
Wherein, in step S2 the temperature of prestripping supersonic reaction device be 40 DEG C, frequency 20000Hz, flow velocity be
3.0m3/ h, circulation stirring speed are 2000r/min, the ultrasonic disperse time is 1.0h；
In step S3 the temperature of twice ultrasonic reaction unit be 40 DEG C, frequency 20000Hz, flow velocity 3.0m3/ h, circulation
Mixing speed is 2000r/min, the ultrasonic disperse time is 4h.
Embodiment 11
The present embodiment provides a kind of preparation method of graphene, comprises the following steps：
S1. the expansion micro crystal graphite being prepared using embodiment 4 is as raw material；
S2. expansion micro crystal graphite obtained by step S1 is placed in prestripping supersonic reaction device and reacted, obtain prestripping
Material；
S3. prestripping material in step S2 is mixed with graphene quantum dot, twice ultrasonic reaction is placed on after 5 times of dilution
Reacted in device, obtain peeling off material；
S4. material press filtration, separation will be peeled off in step S3, then collects Graphite Cake, stripper can then recycle；
S5. clean：Graphite Cake in step S4 is washed with deionized 5 times, obtains graphene；
Wherein, in step S2 the temperature of prestripping supersonic reaction device be 50 DEG C, frequency 25000Hz, flow velocity be
4.0m3/ h, circulation stirring speed are 2000r/min, the ultrasonic disperse time is 0.5h；
In step S3 the temperature of twice ultrasonic reaction unit be 30 DEG C, frequency 25000Hz, flow velocity 5.0m3/ h, circulation
Mixing speed is 2000r/min, the ultrasonic disperse time is 2h.
Comparative example 2
This comparative example provides a kind of preparation method of graphene, is that this comparative example only has one with the difference of embodiment 9
Secondary supersound process, is comprised the following steps that：
S1. the expansion micro crystal graphite being prepared using embodiment 4 is as raw material；
S2. expansion micro crystal graphite obtained by step S1 is mixed with graphene quantum dot, ultrasonic reaction is placed on after 5 times of dilution
Reacted in device, obtain peeling off material；
S3. material press filtration, separation will be peeled off in step S2, then collects Graphite Cake, stripper can then recycle；
S4. clean：Graphite Cake in step S3 is washed with deionized 5 times, obtains graphene；
Wherein, in step S2 the temperature of twice ultrasonic reaction unit be 50 DEG C, frequency 25000Hz, flow velocity 4.0m3/
H, circulation stirring speed be 2000r/min, the ultrasonic disperse time be 3.0h.
Comparative example 3
This comparative example provides a kind of preparation method of graphene, is that this comparative example only has one with the difference of embodiment 9
Secondary supersound process, is comprised the following steps that：
S1. the expansion micro crystal graphite being prepared using embodiment 4 is as raw material；
S2. expansion micro crystal graphite obtained by step S1 is mixed with graphene quantum dot, ultrasonic reaction is placed on after 5 times of dilution
Reacted in device, obtain peeling off material；
S3. material press filtration, separation will be peeled off in step S2, then collects Graphite Cake, stripper can then recycle；
S4. clean：Graphite Cake in step S3 is washed with deionized 5 times, obtains graphene；
In step S3 the temperature of twice ultrasonic reaction unit be 50 DEG C, frequency 25000Hz, flow velocity 5.0m3/ h, circulation
Mixing speed is 2000r/min, the ultrasonic disperse time is 2h.
The graphene that embodiment 9~11 and comparative example 2,3 are prepared carries out AFM test, atomic force
Microscope is used to the lateral dimension and longitudinal thickness of analysis test nanometer two-dimensional material.Specifically, the AFM in this experiment is characterized
It is to be completed by Chinese Marine University, the Ntegra Prima SPM type atomic force microscopies produced using Russian NT-MDT
Mirror, prepare the two-dimentional thickness phenetic analysis of material, and conclusion is as shown in table 1.
Table 1
| Embodiment | Vertical height (nm) | Lateral separation (nm) | Lamella particle diameter (nm) | Lamellar spacing (nm) |
| Embodiment 9 | 2.86 | 351 | 351 | 2.86 |
| Embodiment 10 | 1.89 | 239 | 239 | 1.89 |
| Embodiment 11 | 2.58 | 331 | 331 | 2.58 |
| Comparative example 2 | 3.67 | 427 | 427 | 3.67 |
| Comparative example 3 | 3.98 | 458 | 458 | 3.98 |
As known from Table 1, can tentatively the graphene of projection example 9,10,11 the piece number of plies for 1~5 layer (single-layer graphene
Thickness is 0.334nm).Wherein effect is best in embodiment 9, and the effect of comparative example 2 and comparative example 3 is worst.
Claims (10)
1. a kind of method that micro crystal graphite prepares graphene, it is characterised in that be using micro crystal graphite as raw material, to micro crystal graphite according to
Secondary progress first time chemical graft processing, the processing of first time high temperature puffing, at second of intercalation processing, second of high temperature puffing
Reason, obtains reexpansion micro crystal graphite, then reexpansion micro crystal graphite is ultrasonically treated twice, obtain stripping material, right
Peel off material progress press filtration, separation and cleaning and obtain graphene.
2. the method that micro crystal graphite prepares graphene according to claim 1, it is characterised in that the micro crystal graphite is Chenzhou
City Shandong pool graphite powder, its carbon content are 70 ~ 80%.
3. the method that micro crystal graphite prepares graphene according to claim 1, it is characterised in that comprise the following steps：
S1. micro crystal graphite raw material is taken, crushing and grinding, to the microlite ink powder that granularity is 300 ~ 400 mesh, to microlite ink powder successively
First time intercalation processing, the processing of first time high temperature puffing, second of intercalation processing, second of high temperature puffing processing are carried out, obtains two
Secondary expansion micro crystal graphite；
S2. reexpansion micro crystal graphite obtained by step S1 is placed in prestripping supersonic reaction device and reacted, obtain prestripping
Material；
S3. prestripping material in step S2 is mixed with stripper, is placed in twice ultrasonic reaction unit and reacts after dilution, obtain
To stripping material；
S4. material press filtration, separation will be peeled off in step S3, then collects Graphite Cake, stripper can then recycle；
S5. clean：Graphite Cake in step S4 is cleaned, obtains graphene；
Wherein, in step S2 the temperature of prestripping supersonic reaction device be 30 ~ 50 DEG C, frequency be 10000 ~ 25000 Hz, flow velocity
For 1.0 ~ 4.0m3/ h, circulation stirring speed are 1000 ~ 2000r/min, the ultrasonic disperse time is 0.5 ~ 2.0h, the prestripping
Surface of material is without obvious floating shape thing；
Stripper described in step S3 is graphene quantum dot, and extension rate is 5 times, and the temperature of twice ultrasonic reaction unit is 30
~ 50 DEG C, frequency be 18000 ~ 25000Hz, flow velocity be 2.0 ~ 5.0m3/ h, circulation stirring speed are 1000 ~ 2000r/min, ultrasound
Jitter time is 2 ~ 5h；
Cleaned described in step S5 and refer to use deionized water, wash number is 3 ~ 5 times.
4. the method that micro crystal graphite prepares graphene according to claim 3, it is characterised in that step S1 includes following step
Suddenly：
S11. micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300 ~ 400 mesh are taken；
S12. the potassium permanganate pure with the perchloric acid and chemistry of mass fraction 70% of microlite ink powder obtained by step S1 is placed in reaction
First time chemical graft processing is carried out in device, inflatable micro crystal graphite acidic suspension is obtained, microlite may expand to gained
Black acidic suspension filtering, reservation filtrate is standby, then washs filtrate, dries, obtains and once may expand micro crystal graphite；
S13. micro crystal graphite will be once may expand obtained by step S2 to be placed in graphite expansion stove, is carried out at 800 DEG C high for the first time
Temperature expansion, is once expanded micro crystal graphite；
S14. it is raw material to take appropriate step S3 gained once to expand micro crystal graphite, pure with the concentrated nitric acid and chemistry of mass fraction 65%
Potassium permanganate be placed in reaction unit and carry out second of chemical graft processing, obtain inflatable micro crystal graphite acidic suspension,
The filtering of micro crystal graphite acidic suspension, washing are may expand to gained, is dried, obtains secondary inflatable micro crystal graphite；
S15. secondary inflatable micro crystal graphite obtained by step S4 is placed in graphite expansion stove, carried out at 900 DEG C high second
Temperature expansion, obtains reexpansion micro crystal graphite；
Wherein：It is 30 μm that filter membrane maximum diameter of hole used is filtered described in step S2 and S4；The washing refers to crossing filter residue with 10%
Salt acid elution 3 ~ 5 times, then be washed with deionized to 7 or so；The drying refers to dries 2h under the conditions of 60 ~ 80 DEG C.
5. the method that micro crystal graphite prepares graphene according to claim 4, it is characterised in that described in step S12 for the first time
Chemical graft step includes：
S121. it is 10~30 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；
S122. it is 1 by the mass ratio of the micro crystal graphite powder and potassium permanganate：2~8 add potassium permanganate, stir at room temperature
After mixing uniformly, it is warming up to 30~60 DEG C and continues 1~3.0h of stirring reaction；
S123. add deionized water the temperature in the reaction unit is increased to 60~100 DEG C, be further continued for stirring reaction 1~
3.0h。
6. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 4, it is characterised in that step S13 is in stone
First time high-temperature expansion is carried out in black expansion furnace to comprise the following steps：
S131. feed：Using conserving graphite expanding furnace, an expansible graphite is put into burner hearth by charging aperture, the charging
The temperature of mouth is 30 DEG C, and dispensing speed is 2Kg/h；
S132. expand：The expansion temperature of burner hearth is 800 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S133. discharge：After completing step S132, discharging opening temperature is 50 DEG C, then collects in discharge outlet and is once expanded
Graphite.
7. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 4, it is characterised in that described in step S14
Second of chemical graft step includes：
S141. will once expand micro crystal graphite obtained by step S3 to mix with nitric acid, nitric acid is pressed presses liquid with once expansion micro crystal graphite
Gu than being 1~10：1L/Kg is mixed evenly；
S142. mixed liquor obtained by S141 is mixed with gained filtrate after step S2 filterings and be placed in reaction unit, in room temperature
Under stir after, be warming up to 30~60 DEG C and continue stirring reaction 1~3.0h；
S143. add deionized water, the temperature in the reaction unit is increased to 60~100 DEG C, be further continued for stirring reaction 1~
3.0h。
8. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 4, it is characterised in that step S15 is in stone
Second of high-temperature expansion is carried out in black expansion furnace to comprise the following steps：
S151. feed：Using conserving graphite expanding furnace, expansible graphite is put into burner hearth by charging aperture, the charging aperture
Temperature is 30 DEG C, and dispensing speed is 2Kg/h；
S152. expand：The expansion temperature of burner hearth is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S153. discharge：After completing step S152, discharging opening temperature is 50 DEG C, then collects to obtain reexpansion in discharge outlet
Graphite.
9. the graphene that the method for graphene obtains is prepared according to micro crystal graphite described in claim 1~8 any one.
10. a kind of production system applied to the method for preparing graphene described in claim 1~8 any one in batches, including
Obtain the processing system after secondary expansible graphite, it is characterised in that including conserving graphite expanding furnace, twice ultrasonic device and filtering
Device, conserving graphite expanding furnace are connected with twice ultrasonic device, and twice ultrasonic device is connected with filter；
Conserving graphite expanding furnace includes body of heater, feeding device, drawing mechanism and control device, and expansible graphite passes through feeding device to stove
Body, then collected by drawing mechanism；Drawing mechanism is located above body of heater, and feeding device is located at below body of heater；It is provided with body of heater
Heater, body of heater inner bottom part are additionally provided with air-flow shower nozzle, and air-flow shower nozzle also includes source of the gas, airflow line and control damper, gas
Source connects airflow line, airflow line connection air-flow shower nozzle, and control damper is located in airflow line, is provided with above air-flow shower nozzle
Feeding device, specifically using feed screw, control device includes processor and controller, processor be provided with control panel and with
Controller connects, and controller includes the first controller, second controller and the 3rd controller, the first controller and air-flow shower nozzle
Control damper is connected, and second controller is connected with feeding device, and the 3rd controller is connected with heater;Drawing mechanism and stove
Cooling device is additionally provided between body, cooling device includes heat exchanger tube and water cooling tube, one end connection body of heater of heat exchanger tube, and the other end connects
Drawing mechanism is connect, heat exchanger tube and horizontal angle are 45 DEG C~90 DEG C, and water cooling tube is arranged on heat exchanger tube in the shape of a spiral；Discharging
Device includes multiple reserves storehouses and connecting pipe, and connecting pipe one end is connected with heat exchanger tube, and is provided with cyclone separator, the other end
It is connected with exhaust outlet, multiple subtubes is additionally provided with connecting pipe and are connected respectively with reserves storehouse；Connecting pipe and horizontal folder
Angle is 45 DEG C~90 DEG C；Agitator is additionally provided with body of heater, agitator is spiral agitator, is matched somebody with somebody by motor and ball-screw
Close so that agitator does upper and lower linear motion in body of heater, so as to drive the airflow reflux in body of heater；At the feeding device
Provided with heater；
Twice ultrasonic device includes prestripping device and ultrasonic stripping off device, and prestripping device includes the first batch mixing pond and multiple the
The first circulation system of one ultrasonic reaction kettle composition, the first ultrasonic reaction kettle include Vltrasonic device and reactor, the first batch mixing pond
The dog-house being connected with graphite expansion is provided with, upper end is connected by the first reflux line with the first ultrasonic reaction kettle, lower end point
It is not connected by the first ultrasonic reaction kettle of the first ultrasonic reaction kettle pipeline connection, the first connecting pipe with the first discharge port, first
Ultrasonic reaction kettle pipeline is provided with centrifugal pump and flowmeter, and multiple first ultrasonic reaction kettles are in difference in height arrangement connection, its reclaimed water
Prosposition is put and connected between minimum the first ultrasonic reaction kettle and the first connecting pipe by the first drainage conduit；
The second circulation system that ultrasonic stripping off device includes the second batch mixing pond and multiple second ultrasonic reaction kettles form, the second ultrasound
Reactor includes Vltrasonic device and reactor, and the upper end in the second batch mixing pond is connected by the second reflux line and the second ultrasonic reaction kettle
Connect, lower end is connected with the second connecting tube；Second connecting tube is provided with charging aperture, centrifugal pump, the flow being connected with the first discharge port
Meter and the second discharge port being connected with filter, the second ultrasonic reaction kettle horizontal level is sequentially connected, and is provided with air bleeding valve, and
And it is connected by the second drainage conduit with the second connecting tube；
Filter is plate and frame type filter-press.
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