CN107285306A - A kind of method that micro crystal graphite prepares expansion micro crystal graphite - Google Patents
A kind of method that micro crystal graphite prepares expansion micro crystal graphite Download PDFInfo
- Publication number
- CN107285306A CN107285306A CN201710661667.XA CN201710661667A CN107285306A CN 107285306 A CN107285306 A CN 107285306A CN 201710661667 A CN201710661667 A CN 201710661667A CN 107285306 A CN107285306 A CN 107285306A
- Authority
- CN
- China
- Prior art keywords
- micro crystal
- crystal graphite
- graphite
- expansion
- inflatable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention belongs to technical field of material, more specifically, it is related to a kind of method that micro crystal graphite prepares expansion micro crystal graphite, the present invention is using micro crystal graphite as raw material, first time chemical graft processing being carried out, obtains and once may expand micro crystal graphite, then second of chemical graft processing is carried out again to once may expand micro crystal graphite, secondary inflatable micro crystal graphite, inflatable micro crystal graphite secondary to gained carries out expanded to expand micro crystal graphite using high-temperature expansion method in graphite expansion stove at 900 DEG C.The present invention can prepare high magnification numbe, without sulphur, it is with short production cycle, 200 ~ 260 reexpansion microcrystalline graphite materials can be prepared on a large scale.
Description
Technical field
The invention belongs to technical field of material, more particularly to a kind of expanded graphite prepares expansion micro crystal graphite
Method.
Background technology
Expanded graphite is a kind of carbon material.Expansible graphite is used for raw material, through high temperature (being usually 700~1200 DEG C)
During processing, the material of insertion expanded graphite interlayer is drastically decomposed, and the gas of generation forms high pressure in expansible graphite interlamination region
And expanded along c-axis direction high power, bulk density is changed into 0.003~0.03g/cm3 from 0.7~1.8g/cm3, and expansion multiple reaches
It is tens of to hundreds times.Because intumesced graphite structure is loose, it is porous and in vermiform, surface area is big, and surface can be high, thus has
Excellent liquid phase adsorption performance, good plasticity, preferable pliability, ductility and sealing, therefore be widely used
In the field such as environmental protection, machinery, chemical industry, Aero-Space, atomic energy.
Native graphite has crystalloid (flakey) graphite and crystallite (earthy) graphite, and micro crystal graphite crystal diameter is typically smaller than 1
μm, in crystallite aggregate, sorting is poor, therefore industrially not as crystalline flake graphite is widely used.China's micro crystal graphite resource is rich
Richness, mainly contains on Hebei China, Hunan, Inner Mongol, Shanxi and Jilin and other places, accounts for more than half of global storage capacity.Microlite
Smoky quartz body is tiny, and aggregate is in earthy, without obvious crystalline orientation, in industry such as electronics, machinery, steel, casting, daily-use chemical industries
Field 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,
Particle is small, visible morphon under electron microscope；The latter disperses flakey in monocrystalline, and chip naked eyes are visible.The two is being changed
There is notable difference in terms of reactive nature, crystalline orientation.At present, native graphite is used to prepare expanded graphite for raw material
Raw material used in the technology of material is generally crystalloid flaky graphite.Thus, never have to capture using traditional handicraft and adopt
The technical method of expansion micro crystal graphite is prepared with micro crystal graphite.Also it is few on preparing expansion stone by raw material of micro crystal graphite
The research report of ink material technical method.
Scaly graphite scale is big, aggregate favorable orientation.But, it is necessary to be orientated in battery and electrode material for super capacitor
Property the good graphite material of poor, homogenieity, be that Scaly graphite is often carried out spheroidization processing by this, but result is unsatisfactory.And crystallite
Graphite particle is tiny, and aggregate poor orientation, homogenieity are good, and the expansion micro crystal graphite obtained after expanded processing has more excellent
Different electrical property, this is very important for the use of battery and electrode material for super capacitor etc..
And be related to micro crystal graphite and there was only following two for the patent that raw material prepares expanded graphite：Notification number is
CN103738955A Chinese patent application " a kind of expanded graphite environment-friendly materials and its preparation using Kish graphite as raw material and should
With " a kind of expanded graphite environment-friendly materials preparation method using Kish graphite as raw material is reported,；Notification number is CN104556022A
Chinese patent application " a kind of that the method for expanding microcrystalline graphite material is prepared with micro crystal graphite " report using micro crystal graphite to be former
The method that material prepares expansion microcrystalline graphite material, it is micro- that this patent prepares expanded graphite there is provided one kind using micro crystal graphite as raw material
The method of brilliant material, chemical graft process and high-temperature expansion method are the conventional methods that crystalline flake graphite prepares expanded graphite, but micro-
Difference on spar ink and crystalline flake graphite structure, makes micro crystal graphite prepare the effect of expanded graphite and bad using the method, micro-
The expansion multiple for the expanded graphite that spar ink is prepared is not high, and the entrance containing element sulphur causes product sulfur-bearing during intercalation
Amount is high, and the pernicious gases such as a large amount of sulfur dioxide can be also discharged in expansion process, pollutes environment.
The content of the invention
For reasonable, abundant exploitation micro crystal graphite resource, the technical bottleneck that micro crystal graphite prepares expanded graphite meterial is broken through,
On the basis of micro crystal graphite mineralogy attributes research, the technical method of the present invention is captured, its object is to provide one kind with crystallite
Graphite is that raw material can prepare high magnification numbe, the preparation method without sulphur, reexpansion microcrystalline graphite material with short production cycle.
The purpose of the present invention is achieved by the following technical programs：
A kind of method that micro crystal graphite prepares expansion micro crystal graphite, is, using micro crystal graphite as raw material, to carry out first time chemical graft
Processing, obtains and once may expand micro crystal graphite, then carries out second of chemical graft processing again to once may expand micro crystal graphite,
Secondary inflatable micro crystal graphite, inflatable micro crystal graphite secondary to gained is swollen using high temperature in graphite expansion stove at 900 DEG C
Swollen method progress is expanded must to expand micro crystal graphite.
Preferably, the micro crystal graphite is Chenzhou City Shandong pool graphite powder, and its carbon content is 70 ~ 80%.
Preferably, the method that micro crystal graphite of the present invention prepares expansion micro crystal graphite, including graphite expansion stove, using height
Warm plavini, comprises the following steps：
S1. micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300 ~ 400 mesh are taken；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension；The filtering of micro crystal graphite acidic suspension is may expand to gained, retains filter
Liquid, filter residue is washed, dried, obtains and once may expand micro crystal graphite；
S3. micro crystal graphite will be once may expand obtained by step S2 to be placed in reaction unit with concentrated nitric acid, is then added after S2 filterings
Gained filtrate, carries out second of chemical graft processing, obtains inflatable micro crystal graphite acidic suspension, crystallite is may expand to gained
Graphite acidic suspension is filtered, washs, dried, and obtains secondary inflatable micro crystal graphite
S4. secondary inflatable micro crystal graphite obtained by step S3 is placed in graphite expansion stove, using high-temperature expansion method, expanded
Micro crystal graphite.
Preferably, it is 0.5 ~ 25 μm that filter membrane maximum diameter of hole used is filtered described in step S2 and S3；The washing refers to pair
Filter residue 1 ~ 10% salt acid elution 3 ~ 5 times is crossed, then it is 7 or so to be washed with deionized to ph values；The drying refers at 60 ~ 80 DEG C
Under the conditions of dry 2h.
It is further preferred that first time chemical graft step includes described in step S2：
S21. it is 10~30 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S22. by described micro-
The mass ratio of brilliant graphite composite powder and potassium permanganate is 1：2 ~ 8 add potassium permanganate, be stirred at room temperature it is uniform after, be warming up to 30~
60 DEG C are continued 1~3.0h of stirring reaction；S23. adding deionized water makes the temperature in the reaction unit be increased to 60~100
DEG C, it is further continued for 1~3.0h of stirring reaction.
It is further preferred that second of chemical graft step includes described in step S3：
S31. it is 1~10 by liquid-solid ratio by concentrated nitric acid and microlite ink powder：1L/Kg is added in inflatable acidic suspension, is mixed
Conjunction stirs；S32. adding deionized water makes the temperature in the reaction unit be increased to 90~100 DEG C, is further continued for stirring anti-
Answer 1~3.0h.
It is further preferred that step S4 is comprised the following steps in graphite expansion stove using high-temperature expansion method：
S41. feed：Using conserving graphite expanding furnace, expansible graphite is put into burner hearth by charging aperture, the temperature of the charging aperture
Spend for 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 900 DEG C, is controlled by controlled wind speed swollen
The swollen time is 5s；S43. discharge：Complete after step S42, discharging opening temperature is 50 DEG C, then collect and expanded in discharge outlet
Micro crystal graphite.
The present invention is prepared according to the micro crystal graphite expands the expansion micro crystal graphite that the method for micro crystal graphite is obtained.
Further, the expansion multiple of the expansion micro crystal graphite is 200~260, is wormlike porous material, aperture point
Cloth scope is 1~100nm, and specific surface area is 331~596m2/ g, resistivity is 7.88 × 10-4~9.67 × 10-4Ω•m。
Compared with the prior art, the beneficial effects of the present invention are：
（1）The present invention prepares expansion microcrystalline graphite material using micro crystal graphite, can be further used as preparing the raw material of graphene, carry
A kind of new application of micro crystal graphite is supplied.
（2）The present invention prepares during expansion microcrystalline graphite material creative use intercalation twice using micro crystal graphite
Expansion micro crystal graphite is prepared with reference to high-temperature expansion, the expansion multiple of expansion micro crystal graphite is up to 260 times.
（3）The present invention is added without the material of sulfur-bearing during preparing expansion micro crystal graphite, therefore prepares expansion in high temperature
During micro crystal graphite, sulfur dioxide pollution thing is not produced, the expanded graphite product of preparation also not sulfur-bearing improves expansion stone
The corrosion resistance of ink.
（4）Traditional high-temperature expansion method and graphite expansion stove are combined, used in high-temperature expansion processing procedure by the present invention
Optimal expansion temperature, and the stabilization of product can be effectively improved by the control to raw material and technological parameter around expansion temperature
Property, so as to prepare the controllable expanded graphite of expansion multiple, i.e. the distributive law highest in expansion multiple 200~260, using above-mentioned
Expanded graphite prepares the raw material of graphene as mechanical stripping method, and the stripping rate of graphene can be greatly improved.
（5）Further scientific and reasonable setting of the invention intercalation processing temperature and high-temperature expansion temperature twice, it is ensured that crystallite
The intercalation effect and expansion multiple of graphite, while also remaining original micro crystal graphite structure to greatest extent.
（6）Raw material used in the method for the present invention is cheap, with short production cycle, have obvious social and economic benefits,
It is easily achieved industrialized production.
Brief description of the drawings
Fig. 1 is the high temperature graphite expansion furnace structure figure of embodiment 1 ~ 7.
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.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, adopt
High-temperature expansion method is used, is comprised the following steps：
S1. micro crystal graphite raw material is taken, phosphorus content is 70%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension, and may expand micro crystal graphite acidic suspension to gained filters, and retains filter
Liquid is standby, wherein, first time chemical graft is concretely comprised the following steps：S21. it is by liquid-solid ratio with micro crystal graphite powder by perchloric acid
10：1L/Kg is mixed evenly；S22. it is 2 by the mass ratio of micro crystal graphite powder and strong oxidizer：1 adds strong oxidizer,
After stirring at room temperature, it is warming up to 30 DEG C and continues stirring reaction 3h；S23. adding deionized water makes the temperature in reaction unit
60 DEG C are increased to, stirring reaction 3h is further continued for；
S3. it may expand toward step S2 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out at second of chemical graft
Reason, obtains secondary inflatable micro crystal graphite acidic suspension, and inflatable micro crystal graphite acidic suspension secondary to gained is filtered, washed
Wash, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S31. by concentrated nitric acid with it is micro-
Spar ink powder is 1 by liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；S32. deionization is added
Water makes the temperature in the reaction unit be increased to 90 DEG C, is further continued for stirring reaction 1h.
S4. inflatable micro crystal graphite obtained by step S3 is placed in graphite expansion stove, carries out high-temperature expansion, obtain expansion micro-
Spar ink；Wherein high-temperature expansion is concretely comprised the following steps：S41. feed：Using conserving graphite expanding furnace, expansible graphite is passed through into charging
Mouth is put into burner hearth, and the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth
For 900 DEG C, it is 5s that Bulking Time is controlled by controlled wind speed；S43. discharge：Complete after step S42, discharging opening temperature is 50
DEG C, then collected in discharge outlet and obtain expanding micro crystal graphite.
The expansion multiple of expansion micro crystal graphite is 200 obtained by the present embodiment, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area is 331m2/ g, resistivity is 9.67 × 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 is taken, phosphorus content is 70%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension, and may expand micro crystal graphite acidic suspension to gained filters, and retains filter
Liquid is standby, wherein, first time chemical graft is concretely comprised the following steps：S21. it is by liquid-solid ratio with micro crystal graphite powder by perchloric acid
15：1L/Kg is mixed evenly；S22. it is 4 by the mass ratio of micro crystal graphite powder and strong oxidizer：1 adds strong oxidizer,
After stirring at room temperature, it is warming up to 40 DEG C and continues stirring reaction 2h；S23. adding deionized water makes the temperature in reaction unit
70 DEG C are increased to, stirring reaction 2h is further continued for；
S3. it may expand toward step S2 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out at second of chemical graft
Reason, obtains secondary inflatable micro crystal graphite acidic suspension, and inflatable micro crystal graphite acidic suspension secondary to gained is filtered, washed
Wash, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S31. by concentrated nitric acid with it is micro-
Spar ink powder is 1 by liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；S32. deionization is added
Water makes the temperature in the reaction unit be increased to 90 DEG C, is further continued for stirring reaction 2h.
The expansion multiple of expansion micro crystal graphite is 221 obtained by the present embodiment, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area is 396m2/ g, resistivity is 8.67 × 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 is taken, phosphorus content is 75%, crushing and grinding, to the microlite ink powder that granularity is 350 mesh；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension, and may expand micro crystal graphite acidic suspension to gained filters, and retains filter
Liquid is standby, wherein, first time chemical graft is concretely comprised the following steps：S21. it is by liquid-solid ratio with micro crystal graphite powder by perchloric acid
20：1L/Kg is mixed evenly；S22. it is 6 by the mass ratio of micro crystal graphite powder and strong oxidizer：1 adds strong oxidizer,
After stirring at room temperature, it is warming up to 50 DEG C and continues stirring reaction 2h；S23. adding deionized water makes the temperature in reaction unit
80 DEG C are increased to, stirring reaction 2h is further continued for；
S3. it may expand toward step S2 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out at second of chemical graft
Reason, obtains secondary inflatable micro crystal graphite acidic suspension, and inflatable micro crystal graphite acidic suspension secondary to gained is filtered, washed
Wash, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S31. by concentrated nitric acid with it is micro-
Spar ink powder is 1 by liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；S32. deionization is added
Water makes the temperature in the reaction unit be increased to 90 DEG C, is further continued for stirring reaction 3h.
The expansion multiple of expansion micro crystal graphite is 251 obtained by the present embodiment, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area is 510m2/ g, resistivity is 8.90 × 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 is taken, phosphorus content is 75%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension, and may expand micro crystal graphite acidic suspension to gained filters, and retains filter
Liquid is standby, wherein, first time chemical graft is concretely comprised the following steps：S21. it is by liquid-solid ratio with micro crystal graphite powder by perchloric acid
20：1L/Kg is mixed evenly；S22. it is 6 by the mass ratio of micro crystal graphite powder and strong oxidizer：1 adds strong oxidizer,
After stirring at room temperature, it is warming up to 50 DEG C and continues stirring reaction 1h；S23. adding deionized water makes the temperature in reaction unit
90 DEG C are increased to, stirring reaction 1h is further continued for；
S3. it may expand toward step S2 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out at second of chemical graft
Reason, obtains secondary inflatable micro crystal graphite acidic suspension, and inflatable micro crystal graphite acidic suspension secondary to gained is filtered, washed
Wash, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S31. by concentrated nitric acid with it is micro-
Spar ink powder is 5 by liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；S32. deionization is added
Water makes the temperature in the reaction unit be increased to 100 DEG C, is further continued for stirring reaction 1h.
The expansion multiple of expansion micro crystal graphite is 260 obtained by the present embodiment, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area is 598m2/ g, resistivity is 8.12 × 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 is taken, phosphorus content is 80%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension, and may expand micro crystal graphite acidic suspension to gained filters, and retains filter
Liquid is standby, wherein, first time chemical graft is concretely comprised the following steps：S21. it is by liquid-solid ratio with micro crystal graphite powder by perchloric acid
25：1L/Kg is mixed evenly；S22. it is 7 by the mass ratio of micro crystal graphite powder and strong oxidizer：1 adds strong oxidizer,
After stirring at room temperature, it is warming up to 60 DEG C and continues stirring reaction 1h；S23. adding deionized water makes the temperature in reaction unit
90 DEG C are increased to, stirring reaction 1h is further continued for；
S3. it may expand toward step S2 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out at second of chemical graft
Reason, obtains secondary inflatable micro crystal graphite acidic suspension, and inflatable micro crystal graphite acidic suspension secondary to gained is filtered, washed
Wash, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S31. by concentrated nitric acid with it is micro-
Spar ink powder is 5 by liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；S32. deionization is added
Water makes the temperature in the reaction unit be increased to 100 DEG C, is further continued for stirring reaction 2h.
The expansion multiple of expansion micro crystal graphite is 229 obtained by the present embodiment, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area is 415m2/ g, resistivity is 7.88 × 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 is taken, phosphorus content is 80%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension, and may expand micro crystal graphite acidic suspension to gained filters, and retains filter
Liquid is standby, wherein, first time chemical graft is concretely comprised the following steps：S21. it is by liquid-solid ratio with micro crystal graphite powder by perchloric acid
30：1L/Kg is mixed evenly；S22. it is 8 by the mass ratio of micro crystal graphite powder and strong oxidizer：1 adds strong oxidizer,
After stirring at room temperature, it is warming up to 50 DEG C and continues stirring reaction 1h；S23. adding deionized water makes the temperature in reaction unit
80 DEG C are increased to, stirring reaction 1h is further continued for；
S3. it may expand toward step S2 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out at second of chemical graft
Reason, obtains secondary inflatable micro crystal graphite acidic suspension, and inflatable micro crystal graphite acidic suspension secondary to gained is filtered, washed
Wash, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S31. by concentrated nitric acid with it is micro-
Spar ink powder is 10 by liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；S32. add go from
Sub- water makes the temperature in the reaction unit be increased to 100 DEG C, is further continued for stirring reaction 3h.
The expansion multiple of expansion micro crystal graphite is 233 obtained by the present embodiment, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area is 511m2/ g, resistivity is 8.90 × 10-4Ω•m。
Embodiment 7
The step of the present embodiment, is substantially same as Example 1, and difference is：
S1. micro crystal graphite raw material is taken, phosphorus content is 80%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension, and may expand micro crystal graphite acidic suspension to gained filters, and retains filter
Liquid is standby, wherein, first time chemical graft is concretely comprised the following steps：S21. it is by liquid-solid ratio with micro crystal graphite powder by perchloric acid
30：1L/Kg is mixed evenly；S22. it is 8 by the mass ratio of micro crystal graphite powder and strong oxidizer：1 adds strong oxidizer,
After stirring at room temperature, it is warming up to 50 DEG C and continues stirring reaction 2h；S23. adding deionized water makes the temperature in reaction unit
80 DEG C are increased to, stirring reaction 2h is further continued for；
S3. it may expand toward step S2 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out at second of chemical graft
Reason, obtains secondary inflatable micro crystal graphite acidic suspension, and inflatable micro crystal graphite acidic suspension secondary to gained is filtered, washed
Wash, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S31. by concentrated nitric acid with it is micro-
Spar ink powder is 5 by liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；S32. deionization is added
Water makes the temperature in the reaction unit be increased to 90 DEG C, is further continued for stirring reaction 2h.
The expansion multiple of expansion micro crystal graphite is 253 obtained by the present embodiment, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area is 550m2/ g, resistivity is 7.99 × 10-2Ω•m。
Embodiment 8
It is the graphite expansion stove that the first time high-temperature expansion of embodiment 1 to 7 and second of high-temperature expansion process are used referring to Fig. 1,
Graphite expansion stove includes body of heater 1, feeding device 2, drawing mechanism 3 and control device, and raw material is by feeding device 2 to body of heater 1, so
Collected afterwards by drawing mechanism 3；Drawing mechanism 3 is located above body of heater, and feeding device 2 is located at below body of heater；It is provided with and adds in body of heater 1
Thermal 11, using Resistant heating, the inner bottom part of body of heater 1 is additionally provided with air-flow shower nozzle 4, and air-flow shower nozzle 4 also includes source of the gas 41, air-flow
Pipeline 42 and control damper 43, source of the gas 41 are air, and connect airflow line 42, the connection air-flow of airflow line 42 shower nozzle 4, gas
Flow control valve 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 connected provided with control panel and with controller, and controller includes the first control
Device 53, the controller 51 of second controller 52 and the 3rd, the first controller 53 are connected with the control damper 43 of air-flow shower nozzle 4, the
Two controllers 52 are 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
Valve-driving circuit, the 3rd controller uses heat driven circuit.
Cooling device 7 is additionally provided between drawing mechanism 3 and body of heater 1, cooling device 7 includes 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 horizontal angle are 45 DEG C~90
DEG C, water cooling tube 72 is arranged on heat exchanger tube 71 in the shape of a spiral；
Drawing mechanism 3 includes multiple reserves storehouses 31 and connecting pipe 32, and the one end of connecting pipe 32 is connected with heat exchanger tube 71, and is provided with
Cyclone separator 33, the other end is connected with exhaust outlet 34, be additionally provided with connecting pipe 32 multiple subtubes 35 respectively with reserves storehouse
31 connections；Connecting pipe and 32 horizontal angles are 45 DEG C~90 DEG C；
Agitator 8 is additionally provided with body of heater 1, agitator 8 is spiral agitator, is coordinated by motor and ball-screw so that stir
Mix device 8 done in body of heater 1 above and below linear motion, so as to drive the airflow reflux in body of heater 1.
Wherein：The temperature of discharging opening is controlled by cooling device, and also is provided with heater 6 to control in charging aperture
The temperature of charging aperture processed, specific the present embodiment can be heated using resistance wire 61 to the discharge pipe in feeding device.
By control panel can control expansion time and temperature, specifically processor by control the first controller and
Second controller controls air velocity and charging rate, so as to control the reaction time that intercalated graphite expands, the 3rd controller
The temperature of heater can be controlled, the intellectuality of graphite expansion is realized, reaches and be precisely controlled.
Graphite expansion stove is placed using two floors, is heat exchanger tube and connection from the bottom up according to the processing sequence of raw material
Pipeline and horizontal line have certain angle, by the cooperation of gravity and wind speed, that is, solve expanded graphite and get stuck problem, improve anti-
Yield is answered, while also solving floor space compared to being disposed vertically.
Graphite expansion stove adds agitator 8 in body of heater 1 so that the air-flow formation convection current in body of heater 1, it is ensured that intercalation stone
Black is heated evenly, so that the expanded reaction efficiency of intercalated graphite has been significantly increased
Comparative example 1
Comparative example 1 is with the difference of embodiment 1：High-temperature expansion is without using high-temperature expansion stove, using traditional Muffle furnace, coordinates
High-temperature expansion method, specific different step is as follows：
S4. inflatable micro crystal graphite obtained by step S3 is placed in Muffle furnace and heats calcination process, high temperature is carried out at 900 DEG C swollen
Swollen, Bulking Time is 30s, obtains expanding micro crystal graphite；
The expansion multiple of expansion micro crystal graphite is 190 obtained by the present embodiment, is wormlike porous material, pore size distribution range is 1
~100nm, specific surface area is 498m2/ g, resistivity is 8.65 × 10-4Ω•m。
Claims (9)
1. a kind of method that micro crystal graphite prepares expansion micro crystal graphite, it is characterised in that be, using micro crystal graphite as raw material, to carry out the
Chemical graft processing, obtains and once may expand micro crystal graphite, is then carried out again second to once may expand micro crystal graphite
Chemical graft processing, obtains at secondary inflatable micro crystal graphite, 900 DEG C the inflatable microlite secondary to gained in graphite expansion stove
Ink must expand micro crystal graphite using the progress of high-temperature expansion method is expanded.
2. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 1, it is characterised in that the micro crystal graphite
For Chenzhou City Shandong pool graphite powder, its carbon content is 70 ~ 80%.
3. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 1, it is characterised in that including graphite expansion
Stove, using high-temperature expansion method, comprises the following steps：
S1. micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300 ~ 400 mesh are taken；
S2. microlite ink powder obtained by step S1 and perchloric acid and potassium permanganate are placed in reaction unit and carry out chemical for the first time insert
Layer processing, obtains inflatable micro crystal graphite acidic suspension；
S3. concentrated nitric acid is added toward inflatable micro crystal graphite acidic suspension obtained by step S2, carries out second of chemical graft processing,
Obtain secondary inflatable micro crystal graphite acidic suspension, inflatable micro crystal graphite acidic suspension filtering secondary to gained, washing,
Dry, obtain inflatable micro crystal graphite；
S4. inflatable micro crystal graphite obtained by step S3 is placed in graphite expansion stove, using high-temperature expansion method, obtains expanding crystallite
Graphite.
4. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 3, it is characterised in that in step S2 and S3
Filter membrane maximum diameter of hole used in the filtering is 0.5 ~ 25 μm；The washing refers to crossing filter residue 1 ~ 10% salt acid elution 3 ~ 5 times,
It is 7 or so to be washed with deionized again to ph values；The drying refers to dries 2h under the conditions of 60 ~ 80 DEG C.
5. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 3, it is characterised in that the described in step S2
One time chemical graft step includes：
S21. it is 10~30 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；
S22. it is 1 by the mass ratio of the micro crystal graphite powder and potassium permanganate：2 ~ 8 add potassium permanganate, are stirred at room temperature
After uniform, it is warming up to 30~60 DEG C and continues 1~3.0h of stirring reaction；
S23. add deionized water the temperature in the reaction unit is increased to 60~90 DEG C, be further continued for stirring reaction 1~
3.0h, obtains inflatable micro crystal graphite acidic suspension.
6. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 3, it is characterised in that the described in step S3
Secondary chemical graft step includes：
S31. it is 1~10 by liquid-solid ratio by concentrated nitric acid and microlite ink powder：1L/Kg is added in inflatable acidic suspension, is mixed
Conjunction stirs；
S32. add deionized water the temperature in the reaction unit is increased to 90~100 DEG C, be further continued for stirring reaction 1~
3.0h。
7. the method that micro crystal graphite prepares expansion micro crystal graphite according to claim 3, it is characterised in that step S4 is in graphite
Comprised the following steps in expansion furnace using high-temperature expansion method：
S41. feed：Using conserving graphite expanding furnace, expansible graphite is put into burner hearth by charging aperture, the temperature of the charging aperture
Spend for 30 DEG C, dispensing speed is 2Kg/h；
S42. expand：The expansion temperature of burner hearth is 900 DEG C, and it is 5s that Bulking Time is controlled by controlled wind speed；
S43. discharge：Complete after step S42, discharging opening temperature is 50 DEG C, then collected in discharge outlet and obtain expanding microlite
Ink.
8. the expansion that the method that the micro crystal graphite according to claim 1~7 any one prepares expansion micro crystal graphite is obtained is micro-
Spar ink.
9. reexpansion micro crystal graphite according to claim 8, it is characterised in that the expansion multiple of the expansion micro crystal graphite
It is wormlike porous material for 200~260, pore size distribution range is 1~100nm, and specific surface area is 331~598m2/ g, electricity
Resistance rate is 7.88 × 10-4~9.67 × 10-4Ω•m。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710661667.XA CN107285306A (en) | 2017-08-04 | 2017-08-04 | A kind of method that micro crystal graphite prepares expansion micro crystal graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710661667.XA CN107285306A (en) | 2017-08-04 | 2017-08-04 | A kind of method that micro crystal graphite prepares expansion micro crystal graphite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107285306A true CN107285306A (en) | 2017-10-24 |
Family
ID=60105246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710661667.XA Pending CN107285306A (en) | 2017-08-04 | 2017-08-04 | A kind of method that micro crystal graphite prepares expansion micro crystal graphite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107285306A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597061A (en) * | 2017-10-31 | 2018-01-19 | 湖南国盛石墨科技有限公司 | It is a kind of to be used to remove Nanoscale Iron/exfoliated-graphite composite of Heavy Metals in Waters and preparation method thereof |
| CN107658464A (en) * | 2017-10-31 | 2018-02-02 | 湖南国盛石墨科技有限公司 | Preparation method for phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite of lithium ion battery |
| CN107651682A (en) * | 2017-10-31 | 2018-02-02 | 湖南国盛石墨科技有限公司 | A kind of preparation method of mixed expanded graphite |
| CN107785556A (en) * | 2017-10-31 | 2018-03-09 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the dilute nanometer sheet of micro crystal graphite/silicon combination electrode material |
| CN107799774A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material |
| CN107799753A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of method that phosphoric acid vanadium lithium/expansion micro crystal graphite combination electrode material is prepared in Metal Substrate |
| CN107799752A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of preparation method of nano oxidized iron particle/expansion micro crystal graphite composite for lithium ion battery |
| CN107845795A (en) * | 2017-10-31 | 2018-03-27 | 湖南国盛石墨科技有限公司 | A kind of CNT/micro- swollen graphite combination electrode material and preparation method thereof |
| CN107919477A (en) * | 2017-12-22 | 2018-04-17 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium ion battery negative material |
| CN108054024A (en) * | 2017-12-22 | 2018-05-18 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium-ion capacitor negative material |
| CN108063234A (en) * | 2017-12-22 | 2018-05-22 | 林荣铨 | A kind of carbon nanotubes/application of micro- swollen graphite composite material as lithium ion battery negative material |
| CN108063055A (en) * | 2017-12-23 | 2018-05-22 | 林荣铨 | A kind of lithium-ion capacitor |
| CN113735113A (en) * | 2021-10-21 | 2021-12-03 | 青岛洛唯新材料有限公司 | Expandable graphite and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556022A (en) * | 2015-01-27 | 2015-04-29 | 西南科技大学 | Method for preparing expanded microcrystal graphite material from microcrystal graphite |
| CN106744924A (en) * | 2016-12-16 | 2017-05-31 | 北京鼎臣超导科技有限公司 | A kind of preparation method of expanded graphite |
-
2017
- 2017-08-04 CN CN201710661667.XA patent/CN107285306A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556022A (en) * | 2015-01-27 | 2015-04-29 | 西南科技大学 | Method for preparing expanded microcrystal graphite material from microcrystal graphite |
| CN106744924A (en) * | 2016-12-16 | 2017-05-31 | 北京鼎臣超导科技有限公司 | A kind of preparation method of expanded graphite |
Non-Patent Citations (1)
| Title |
|---|
| 蒋述兴等: "二次插层制备可膨胀石墨的实验研究", 《非金属矿》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597061A (en) * | 2017-10-31 | 2018-01-19 | 湖南国盛石墨科技有限公司 | It is a kind of to be used to remove Nanoscale Iron/exfoliated-graphite composite of Heavy Metals in Waters and preparation method thereof |
| CN107658464A (en) * | 2017-10-31 | 2018-02-02 | 湖南国盛石墨科技有限公司 | Preparation method for phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite of lithium ion battery |
| CN107651682A (en) * | 2017-10-31 | 2018-02-02 | 湖南国盛石墨科技有限公司 | A kind of preparation method of mixed expanded graphite |
| CN107785556A (en) * | 2017-10-31 | 2018-03-09 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the dilute nanometer sheet of micro crystal graphite/silicon combination electrode material |
| CN107799774A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material |
| CN107799753A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of method that phosphoric acid vanadium lithium/expansion micro crystal graphite combination electrode material is prepared in Metal Substrate |
| CN107799752A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of preparation method of nano oxidized iron particle/expansion micro crystal graphite composite for lithium ion battery |
| CN107845795A (en) * | 2017-10-31 | 2018-03-27 | 湖南国盛石墨科技有限公司 | A kind of CNT/micro- swollen graphite combination electrode material and preparation method thereof |
| CN107919477A (en) * | 2017-12-22 | 2018-04-17 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium ion battery negative material |
| CN108054024A (en) * | 2017-12-22 | 2018-05-18 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium-ion capacitor negative material |
| CN108063234A (en) * | 2017-12-22 | 2018-05-22 | 林荣铨 | A kind of carbon nanotubes/application of micro- swollen graphite composite material as lithium ion battery negative material |
| CN108063055A (en) * | 2017-12-23 | 2018-05-22 | 林荣铨 | A kind of lithium-ion capacitor |
| CN108063055B (en) * | 2017-12-23 | 2020-04-07 | 林荣铨 | Lithium ion capacitor |
| CN113735113A (en) * | 2021-10-21 | 2021-12-03 | 青岛洛唯新材料有限公司 | Expandable graphite and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107285306A (en) | A kind of method that micro crystal graphite prepares expansion micro crystal graphite | |
| CN104556022B (en) | It is a kind of that the method for expanding microcrystalline graphite material is prepared with micro crystal graphite | |
| CN107285307A (en) | A kind of method that micro crystal graphite prepares reexpansion micro crystal graphite | |
| CN107381566A (en) | A kind of method that micro crystal graphite prepares reexpansion micro crystal graphite | |
| CN102145913A (en) | Preparation method of nano spherical yttrium oxide powder for thermal spraying | |
| CN210486365U (en) | System for drying iron phosphate by using waste heat of roasting furnace | |
| CN103072961A (en) | Production method of nano aluminum nitride powder | |
| CN104600248A (en) | Silicon-base negative material for lithium ion battery and preparation method of silicon-base negative material | |
| CN103754865B (en) | The preparation method of village hollowing graphite material and prepared village hollowing graphite material thereof | |
| CN108946824A (en) | A kind of preparation method of big granularity cobaltosic oxide | |
| CN107337804A (en) | A kind of PET/ micro crystal graphites alkene composite heat conducting film and preparation method thereof | |
| CN107352531A (en) | A kind of method that micro crystal graphite prepares graphene | |
| CN107651682A (en) | A kind of preparation method of mixed expanded graphite | |
| CN107293708A (en) | The improved method that solvent-thermal method prepares graphene silicon composite | |
| CN106699550A (en) | Preparation method of nano Cu-CuBTC type metal organic framework material | |
| CN107522890A (en) | A kind of PET/ micro crystal graphites alkene composite heat conducting film and preparation method thereof | |
| CN103882558B (en) | A kind of perovskite structure AgNbO 3fiber and preparation method thereof | |
| CN107799752A (en) | A kind of preparation method of nano oxidized iron particle/expansion micro crystal graphite composite for lithium ion battery | |
| CN107658464A (en) | Preparation method for phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite of lithium ion battery | |
| CN107662917A (en) | A kind of micro crystal graphite prepares graphene method | |
| CN107785556A (en) | A kind of preparation method of the dilute nanometer sheet of micro crystal graphite/silicon combination electrode material | |
| CN107814404A (en) | A kind of production method of cube nano-calcium carbonate | |
| CN207845500U (en) | A kind of strength gaseous suspension cooling device for producing powdery active lime system | |
| CN110330008A (en) | A kind of continuous producing method of carbon nanotube | |
| CN107597061A (en) | It is a kind of to be used to remove Nanoscale Iron/exfoliated-graphite composite of Heavy Metals in Waters and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171024 |
|
| RJ01 | Rejection of invention patent application after publication |