CN104843690B - Method for preparing graphene by means of steam explosion method - Google Patents
Method for preparing graphene by means of steam explosion method Download PDFInfo
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- CN104843690B CN104843690B CN201510213046.6A CN201510213046A CN104843690B CN 104843690 B CN104843690 B CN 104843690B CN 201510213046 A CN201510213046 A CN 201510213046A CN 104843690 B CN104843690 B CN 104843690B
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Abstract
A method for preparing graphene by means of a steam explosion method comprises the following steps of 1 using graphene to prepare oxidized graphene, 2 mixing the prepared oxidized graphene and dispersion liquid and performing ultrasonic dispersion and stirring to obtain an oxidized graphene solution; 3 arranging the oxidized graphene solution in a steam explosion pressure relief valve, controlling temperature rising rate to be 5 DEG C/min-15 DEG C/min, rising the temperature to be 300 DEG-500 DEG C, keeping the temperature for 2-10 hours and then instantly releasing pressure to obtain a reaction product; 4 washing and drying the reaction product to obtain the graphene. The method is simple in operation, short in preparation time, free of pollution, low in cost and high in yield, can be used for lithium battery electrode materials and lubricating materials, can be also used for medicine, catalysis or special spraying materials and can be directly used as or synthesized into an abrasion-resisting material for an engine air cylinder.
Description
Technical field
The present invention relates to grapheme material field, particularly a kind of method for preparing Graphene with steam explosion method.
Background technology
Graphene be one kind by carbon atom with sp2Hybrid orbital composition hexangle type is in the flat film of honeycomb lattice, only has
The two-dimensional material of one carbon atom thickness, is most thin, the most hard nano material in known world.It is almost fully transparent
, only absorb 2.3% light；Heat conductivity is up to 5300 W/m K, and higher than CNT and diamond, under room temperature, its electronics is moved
Shifting rate is more than 15000 cm2/ V s, but it is higher than CNT or silicon crystal, and resistivity about 10-8Ω cm, than copper or silver
It is lower, it is the minimum material of world resistivity, particularly theoretical specific surface area 2630m with super large2/g。
Graphene possesses huge application prospect, and this requires to find a kind of quick, efficient, cheap preparation method to expire
The growing demand of foot.Current Graphene production capacity both at home and abroad is low, the situation generally existing that quality is unstable, is employingization mostly
Method prepares Graphene, and this performance impact to Graphene is very big, while existing, environmental pollution is serious, cost of material is high, anti-
The problems such as answering condition harshness, yield poorly, practicality is not strong.
CN201310262842.X discloses a kind of method that foaming and intumescing method prepares Graphene, and which adopts Graphene/poly-
Urethane composite prepares Graphene, and preparation process does not use strong oxidizing property, strong and stimulating material；But the method operation is drawn
New chemical substance is entered, has increased cost, and preparation time is long, be unfavorable for that fast industrialization is produced.
The content of the invention
The purpose of the present invention is to overcome the above-mentioned not enough of prior art and provide a kind of simple to operate, and preparation time is short, nothing
Pollution, low cost, the high method that Graphene is prepared with steam explosion method of yield.
The technical scheme is that：
A kind of method for preparing Graphene with steam explosion method, comprises the following steps：
（1）Graphene oxide is prepared using graphite；
（2）Ultrasonic disperse is carried out after the graphene oxide for having prepared is mixed with dispersion liquid and is stirred, obtain graphite oxide
Alkene solution；
（3）Graphene oxide solution is placed in steam explosion relief valve, it is 5 DEG C/min～15 DEG C/min to control heating rate,
300 DEG C～500 DEG C are warming up to, moment release after insulation 2h～10h obtains product；
（4）Graphene is obtained by product washing, after being dried.
Further, the step of use graphite prepares graphene oxide includes：
（1）300 ~ 500ml strong acid is added in a kettle., 6g graphite is added, and room temperature is stirred 1 hour；
（2）0 ~ 16g of oxidant is added, is stirred 2 hours, is obtained mixture；
（3）Mixture is centrifuged, gained filtering residue adopts pure water twice；
（4）Hydrogen peroxide 5ml is added in washed filtering residue, is added water and is stirred and washing and filter pressing, obtain aoxidizing stone
Black alkene.
Further, the strong acid is one or more of sulphuric acid, chlorosulfonic acid, phosphoric acid, nitric acid, fluosulfonic acid, and the concentration of acid is not
Less than 50%.
Further, the oxidant be potassium permanganate, potassium iodate, one or more in potassium ferrate.
Further, the centrifugal speed when mixture is centrifuged is 8000 ~ 10000rpm, and centrifugation time is 10 ~ 20min；
Mixture centrifugation centrifugal liquid used is reusable.
Further, step（2）In, the graphene oxide for having prepared is mixed with dispersion liquid to carry out ultrasonic disperse and stirs
20min, obtains graphene oxide solution.
Further, the steam explosion relief valve includes valve seat, valve body and the valve gap installed successively from top to bottom, the valve seat with
Heated base is provided between valve body, is provided with piston type flap above the heated base, the piston type flap connection valve bar,
The end of the valve rod connects stage clip after passing through valve body and valve gap.
Further, the graphene oxide solution is entered from the entrance of heated base, control heating rate be 5 DEG C/min～
15℃/min（Preferably 6 DEG C/min～9 DEG C/min, more preferably 10 DEG C/min～14 DEG C/min）, it is warming up to 300 DEG C～500
℃（Preferably 350 DEG C～400 DEG C, more preferably 430 DEG C～480 DEG C）, the gases at high pressure promotion piston type flap of generation is upwards
Mobile, stage clip is bent by valve rod, 2h～10h to be incubated（Preferably 3h～5h, more preferably 6h～9h）Afterwards, open going out for valve body
QI KOU carries out release, i.e., obtain product in heated base.
Further, it is described that graphene oxide solution is placed in steam explosion relief valve, heating rate is controlled for 6 DEG C/min～9
DEG C/min, and 350 DEG C～400 DEG C are warming up to, moment release after insulation 3h～5h obtains product.
Further, it is described that graphene oxide solution is placed in steam explosion relief valve, control heating rate for 10 DEG C/min～
14 DEG C/min, 430 DEG C～480 DEG C are warming up to, moment release after insulation 6h～9h obtains product.
The present invention has following features compared with prior art：Graphite is peeled off by high speed and obtains graphene oxide, utilized
Pressure expansion strip off graphene sheet layer, simple to operate, preparation time is short, pollution-free, low cost, and yield is high, can be used for lithium battery
Electrode material, lubriation material, it can also be used to medicine, are catalyzed or do extraordinary sprayed on material（Such as non-stick cooker, glass with clean plated film
Deng）, can also directly or synthesis do high-abrasive material of cylinder etc..
Description of the drawings
Structural representations of the Fig. 1 for embodiment of the present invention reactor；
Fig. 2 is structural representation when embodiment of the present invention steam explosion relief valve does not work；
Fig. 3 is structural representation when embodiment of the present invention steam explosion relief valve works；
Fig. 4 is the SEM electron microscopic pictures of Graphene prepared by the embodiment of the present invention.
Specific embodiment
The detailed construction of the present invention is further described below in conjunction with the drawings and specific embodiments.
Device embodiment：
Embodiment 1
Graphene oxide is prepared in reactor.As shown in Figure 1：Reactor includes vessel 1, vessel 1
Upper end side be provided with charge door 11, bottom is provided with discharging opening 12, and middle part is provided with motor 2, and the bottom of motor 2 is provided with rotor 3,
The outside of rotor 3 is provided with stator 4.Graphite can quickly be peeled off by the high speed centrifugation operation of rotor 3, graphite oxide is prepared
Alkene, shortens preparation time.
Embodiment 2
Graphene is prepared in steam explosion relief valve.As shown in Figure 2：Steam explosion relief valve includes installing successively from top to bottom
Valve seat 5, valve body 6 and valve gap 7, be provided with heated base 8 between valve seat 5 and valve body 6, the top of heated base 8 is provided with piston type
Flap 61, the connection valve rod 62 of piston type flap 61, the end of valve rod 62 connects stage clip 9 after passing through valve body 6 and valve gap 7.
During work, as shown in Figure 3：Graphene oxide solution is pumped into by steam explosion relief valve from the porch of heated base 8, Jing
Heating obtains High Temperature High Pressure, and then promotes piston type flap 61 to move upwards, and stage clip 9 is bent by valve rod 62；Using pressure expansion
Strip off graphene sheet layer, after pushing aside completely, the gas outlet for opening valve body 6 carries out release, so as to obtain Graphene.Using steam explosion
Relief valve prepares Graphene and can shorten preparation time, and forms confined space when working in valve body 6, and safety coefficient is high, without dirt
Dye, prepared Graphene yield are high.
Embodiment of the method：
Embodiment 1
（1）400ml, 98% sulphuric acid is added in a kettle., adds 6g graphite, room temperature to stir 1 hour, add Gao Meng
Sour potassium 12g, stirs 2 hours；（2）With the rotating speed centrifugation 20min of 8000rpm, centrifugal liquid is reusable, and centrifugation gained filtering residue is used
Pure water adds hydrogen peroxide 5ml twice, in washed filtering residue, adds water and stirs and washing and filter pressing, is aoxidized
Graphene；（3）Ultrasonic disperse is carried out after graphene oxide is mixed with dispersion liquid and is stirred, obtain graphene oxide solution；（4）
Proceed in steam explosion relief valve, it is 5 DEG C/min～10 DEG C/min to control heating rate, is warming up to 300 DEG C～500 DEG C, insulation 2h～
Moment release after 4h, obtains product；Graphene will be obtained after product washing, drying again, as shown in Figure 4.
Embodiment 2
The present embodiment with the difference of embodiment 1 is：It is 6 DEG C/min～15 DEG C/min to control heating rate, is warming up to 350
DEG C～500 DEG C, it is incubated 2h～4h.Other are same as Example 1.
Embodiment 3
The present embodiment with the difference of embodiment 1 is：It is 6 DEG C/min～9 DEG C/min to control heating rate, is warming up to 350
DEG C～400 DEG C, it is incubated 3h～5h.Other are same as Example 1.
Embodiment 4
The present embodiment with the difference of embodiment 1 is：It is 10 DEG C/min～14 DEG C/min to control heating rate, is warming up to
430 DEG C～480 DEG C, it is incubated 6h～9h.Other are same as Example 1.
Embodiment 5
The present embodiment from unlike specific embodiment 1：It is 8 DEG C/min～10 DEG C/min to control heating rate, is warming up to
320 DEG C～400 DEG C, it is incubated 3h～6h.Other are same as Example 1.
Embodiment 6
The present embodiment from unlike specific embodiment 1：It is 7 DEG C/min～12 DEG C/min to control heating rate, is warming up to
420 DEG C～450 DEG C, it is incubated 3h～5h.Other are same as Example 1.
Embodiment 7
The present embodiment from unlike specific embodiment 1：It is 7 DEG C/min～14 DEG C/min to control heating rate, is warming up to
460 DEG C～490 DEG C, it is incubated 2h～3h.Other are same as Example 1.
Embodiment 8
The present embodiment from unlike specific embodiment 1：It is 9 DEG C/min～12 DEG C/min to control heating rate, is warming up to
310 DEG C～350 DEG C, it is incubated 2h.Other are same as Example 1.
Embodiment 9
The present embodiment from unlike specific embodiment 1：It is 10 DEG C/min～12 DEG C/min to control heating rate, is warming up to
360 DEG C～400 DEG C, it is incubated 4h.Other are same as Example 1.
Embodiment 10
The present embodiment from unlike specific embodiment 1：It is 13 DEG C/min～15 DEG C/min to control heating rate, is warming up to
410 DEG C～450 DEG C, it is incubated 5h.Other are same as Example 1.
The yield of Graphene prepared by the method for the present embodiment 1 ~ 10 is adopted for 5g ~ 6g.
The preferred embodiments of the present invention are these are only, the present invention is not limited to, it is clear that those skilled in the art can
To carry out various changes, modification without departing from the spirit and scope of the present invention to the present invention.If these modifications to the present invention
Belong within the scope of the claims in the present invention and its equivalent technologies with modification, belong to protection scope of the present invention.
Claims (9)
1. a kind of method that Graphene is prepared with steam explosion method, it is characterised in that：Comprise the following steps：
（1）Graphene oxide is prepared using graphite；
（2）Ultrasonic disperse is carried out after the graphene oxide for having prepared is mixed with dispersion liquid and is stirred, obtain graphene oxide molten
Liquid；
（3）Graphene oxide solution is placed in steam explosion relief valve, heating rate is controlled for 5 DEG C/min～15 DEG C/min, intensification
To 300 DEG C～500 DEG C, moment release after insulation 2h～10h obtains product；
（4）Graphene is obtained by product washing, after being dried；
The steam explosion relief valve includes valve seat, valve body and the valve gap installed successively from top to bottom, sets between the valve seat and valve body
There is heated base, above the heated base, be provided with piston type flap, the piston type flap connection valve bar, the valve rod
End connects stage clip after passing through valve body and valve gap.
2. the method for Graphene being prepared with steam explosion method according to claim 1, it is characterised in that：The use graphite prepares oxygen
The step of graphite alkene, includes：
（1）300 ~ 500ml strong acid is added in a kettle., 6g graphite is added, and room temperature is stirred 1 hour；
（2）0 ~ 16g of oxidant is added, is stirred 2 hours, is obtained mixture；
（3）Mixture is centrifuged, gained filtering residue adopts pure water twice；
（4）Hydrogen peroxide 5ml is added in washed filtering residue, is added water and is stirred and washing and filter pressing, obtains graphene oxide.
3. the method for Graphene being prepared with steam explosion method according to claim 2, it is characterised in that：The strong acid is sulphuric acid, chlorine
One or more of sulfonic acid, phosphoric acid, nitric acid, fluosulfonic acid, the concentration of acid are not less than 50%.
4. the method for Graphene being prepared with steam explosion method according to Claims 2 or 3, it is characterised in that：The oxidant is height
One or more in potassium manganate, potassium iodate, potassium ferrate.
5. the method for Graphene being prepared with steam explosion method according to Claims 2 or 3, it is characterised in that：The mixture centrifugation
When centrifugal speed be 8000 ~ 10000rpm, centrifugation time be 10 ~ 20min；Mixture centrifugation centrifugal liquid used is repeatable to be made
With.
6. the method for Graphene being prepared with steam explosion method according to claim 1, it is characterised in that：Step（2）In, prepared
Graphene oxide mix with dispersion liquid and carry out ultrasonic disperse and stir 20min, obtain graphene oxide solution.
7. the method for Graphene being prepared with steam explosion method according to claim 1 or 2 or 3, it is characterised in that：The graphite oxide
Alkene solution is entered from the entrance of heated base, and it is 5 DEG C/min～15 DEG C/min to control heating rate, is warming up to 300 DEG C～500
DEG C, the gases at high pressure of generation promote piston type flap to move up, and stage clip is bent by valve rod, after insulation 2h～10h, open valve
The gas outlet of body carries out release, i.e., obtain product in heated base.
8. the method for Graphene being prepared with steam explosion method according to claim 1 or 2 or 3, it is characterised in that：It is described to aoxidize stone
Black alkene solution is placed in steam explosion relief valve, and it is 6 DEG C/min～9 DEG C/min to control heating rate, is warming up to 350 DEG C～400 DEG C, is protected
After warm 3h～5h, moment release, obtains product.
9. the method for Graphene being prepared with steam explosion method according to claim 1 or 2 or 3, it is characterised in that：It is described to aoxidize stone
Black alkene solution is placed in steam explosion relief valve, and it is 10 DEG C/min～14 DEG C/min to control heating rate, is warming up to 430 DEG C～480 DEG C,
Moment release after insulation 6h～9h, obtains product.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105752964A (en) * | 2016-01-25 | 2016-07-13 | 肖荣阁 | High-temperature high-pressure bursting method for producing graphene and equipment |
| CN106517168A (en) * | 2016-11-10 | 2017-03-22 | 中国石油大学(北京) | Device and method for preparing graphene by exfoliating graphite through quick pressure relief |
| CN107032338B (en) * | 2017-06-19 | 2018-03-09 | 成都新柯力化工科技有限公司 | A kind of method of continuous discharge-induced explosion parallel off preparing graphite alkene |
| CN110156002B (en) * | 2019-06-04 | 2023-02-10 | 新疆弘瑞达纤维有限公司 | Preparation method of graphene oxide material |
| CN111498838A (en) * | 2020-05-12 | 2020-08-07 | 山东领军科技集团有限公司 | Graphene wet-process air pressure stripping method |
| CN115124033B (en) * | 2022-06-30 | 2024-03-29 | 哈尔滨石油学院 | Graphene stripping device and graphene preparation method |
| CN115536016A (en) * | 2022-10-12 | 2022-12-30 | 三门峡芳瑞杜仲产业技术研究院有限公司 | Physical graphene stripping method |
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| CN1708455A (en) * | 2002-11-05 | 2005-12-14 | 株式会社Ohc碳 | Process for producing nano substance through vapor explosion, apparatus therefor and process for producing nano raw material |
| CN102491314A (en) * | 2011-11-24 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
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