CN107758656A - A kind of system and method for two-period form co-production coal base graphite and CNT - Google Patents
A kind of system and method for two-period form co-production coal base graphite and CNT Download PDFInfo
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- CN107758656A CN107758656A CN201711086932.2A CN201711086932A CN107758656A CN 107758656 A CN107758656 A CN 107758656A CN 201711086932 A CN201711086932 A CN 201711086932A CN 107758656 A CN107758656 A CN 107758656A
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Abstract
The present invention provides a kind of system and method for two-period form co-production coal base graphite and CNT, the system includes graphitization module and CNT generation module, graphitization module includes graphitization reactor, and the roof of graphitization reactor is provided with volatilize sub-export, bottom wall and is provided with current-carrying gas import；CNT generation module includes reforming reactor, and the roof of reforming reactor is provided with volatile matter import and vapor import provided with waste gas outlet, bottom wall；Upper and lower sieve plate is respectively equipped with graphitization reaction and reforming reactor, and feed inlet and outlet is equipped with the side wall of two reactors；Volatilization sub-export is connected with volatile matter import by intermediate conduit.Have the beneficial effect that, for coal high temperature graphitization high energy consumption in the prior art and fail effectively to utilize the deficiency of volatile matter in graphitizing process, effectively combined by the reaction that catalyzed graphitization and catalytic reforming are prepared to CNT, while realizing coal resource cascade utilization, the product of high attached value is obtained.
Description
Technical field
The invention belongs to coal resourceization to utilize and carbon material preparation field, and in particular to a kind of two-period form co-production coal base
The system and method for graphite and CNT.
Background technology
Graphite is a kind of excellent carbon material, has good heat endurance, thermal conductance, lubricity and chemically stable
Property, it is widely used in fields such as metallurgical, machinery, electric, chemical industry.Because demand is big, native graphite can not meet the mankind
Use demand, this causes Delanium to receive much concern.Now, graphite is industrially manufactured mainly in the bar of 2500 DEG C or so anoxybiotics
The carbon raw material such as calcined petroleum coke, pitch coke, anthracite under part, too high temperature have aggravated to produce the cost of graphite.Therefore, such as
It is always the important directions for producing graphite research that what, which reduces reaction temperature and then reduces production cost,.Research shows, by stone
The simple substance and its compound that the elements such as Fe, Cu, B are added during inkization can effectively reduce required temperature 900 as catalyst
More than DEG C.
One-dimensional carbon material of the CNT as uniqueness, with excellent mechanics, electromagnetism, optics and thermodynamic property
It is widely used in every field.Main method prepared by CNT has arc process, laser evaporization method, plasma method and urged
Change chemical deposition etc..Catalytic chemistry sedimentation be considered as most it is potential realize extensive, low cost, yield it is high prepare carbon
The method of nanotube.In the presence of catalyst, carbonaceous gas is catalytically decomposed to form CNT.Now, how more efficient,
Production CNT becomes the problem of receiving much concern at low cost.
The content of the invention
The present invention provides a kind of system and method for two-period form co-production coal base graphite and CNT, it is intended to passes through two
Segmentation structure, CNT is prepared on the basis of catalyzed graphitization is realized using catalytic reforming reaction, so as to realize coal resource
Cascade utilization, reduce the cost of whole technique.
The present invention realizes that the technical scheme of above-mentioned target is as follows：A kind of two-period form co-production coal base graphite and CNT
System, it includes graphitization module and CNT generation module, wherein：
The graphitization module includes graphitization reactor, and upper sieve plate is provided with roof in the graphitization reactor
First, lower sieve plate one is provided with bottom wall, the roof of the graphitization reactor is provided with volatilization sub-export, bottom wall provided with load
Gas import, the side wall of the graphitization reactor are provided with feed inlet and outlet one, and the feed inlet and outlet one is located at the lower sieve plate
One top；
The CNT generation module includes reforming reactor, and upper sieve is provided with roof in the reforming reactor
Plate two, lower sieve plate two is provided with bottom wall, the roof of the reforming reactor is provided with waste gas outlet, bottom wall provided with volatilization
Divide import and vapor import, the side wall of the reforming reactor is provided with feed inlet and outlet two, and the feed inlet and outlet two is located at institute
State the top of lower sieve plate two；
The volatilization sub-export is connected with the volatile matter import by intermediate conduit, and exhaust is provided with the waste gas outlet
Valve, the current-carrying gas import connect with current-carrying gas input channel, and the vapor import connects with vapor input channel, institute
State and door body able to turn on or off is respectively equipped with feed inlet and outlet one and the feed inlet and outlet two, the graphitization reactor and reforming reaction
Electrothermal heating component is respectively equipped with device.
On the basis of above-mentioned technical proposal, the present invention can also have following further improvement.
Further, the intermediate conduit is provided with the air valve to the reforming reactor one-way conduction.
Setting the air valve of one-way conduction is advantageous in that, it is ensured that current-carrying gas carries volatile matter and is smoothly passed through reforming reactor
In, while prevent that volatile matter and vapor into reforming reactor from flowing back to graphitization reactor.
Further, the current-carrying gas input channel connects with nitrogen cylinder or inert gas steel cylinder.
It should be noted that for the ease of being controlled to the total amount and intake velocity that are passed through current-carrying gas, the gas that dams input
Control valve and flow (flow velocity) should be set to count on pipeline.
Further, the vapor input channel connects with the vapor outlet port of boiler-steam dome.
It should be noted that if the pressure deficiency in drum, can be set booster pump on vapor input channel, to incite somebody to action
In vapor press-in reforming reactor.
Further, the electrothermal heating component includes heating wire or electric hot plate and the heating wire or electric hot plate are close to described
Lower sieve plate one and lower sieve plate two are set.
Because graphitization reaction or reforming reaction are mainly carried out on lower sieve plate one and lower sieve plate two respectively, therefore electrothermal heating
Component should be arranged on lower sieve plate one and lower sieve plate two nearby to ensure the heat of more preferable supply response needs.
In addition, present invention also offers carry out two-period form co-production coal base graphite and CNT using above-mentioned system
Method, it comprises the following steps：
S1. by coal dust and catalyst one according to 5-20:After 1 mass ratio is sufficiently mixed, by feed inlet and outlet one add to
In the graphitization reactor, while catalyst two, coal dust and catalysis are added into the reforming reactor from feed inlet and outlet two
The mass ratio of agent two is 5-20:1；
S2. the door body closed at the feed inlet and outlet one and feed inlet and outlet two, it is anti-from the import of current-carrying gas to the graphitization
Answer device to be passed through current-carrying gas, discharge the air in graphitization reactor and reforming reactor, continue logical current-carrying gas, graphite is respectively started
Change the electrothermal heating component in reactor and reforming reactor, when graphitization reactor is warming up to 900 DEG C, reforming reactor
Temperature control is 550-900 DEG C, now closes waste gas outlet and is passed through water steaming into the reforming reactor from vapor import
Gas, stop after 10-15min being passed through vapor, while stop being passed through current-carrying gas, the gross mass for the vapor being passed through is quality of pc
5-30%；
S3. in the graphitization reactor since when its temperature rises to 900 DEG C, it is 900-1600 to maintain its interior temperature
DEG C, 1-3h is reacted, the temperature control in interior reforming reactor is 550-900 DEG C therebetween herein, since being passed through vapor, is reformed
Reaction continues 1-3h, and reaction is down to normal temperature after terminating, and waste gas outlet exhaust is then opened, through feed inlet and outlet one and feed inlet and outlet two
The product on the product and lower sieve plate two on lower sieve plate one is taken out, coal base graphite and CNT are respectively obtained after purified.
On the basis of above-mentioned technical proposal, the present invention can also have following further more specific or more excellent scheme choosing
Select.
Preferably, coal dust, catalyst one and catalyst two are before addition by grinding and drying process, coal dust, catalysis
Particle diameter after agent one and catalyst two are ground is 20-100 mesh.
Specifically, catalyst one is one in Fe, Ni, Mn, Mg, Zn, Ca, W, Cu and B simple substance, oxide, chloride
Kind or a variety of mixing.Catalyst one can ensure that graphitization is carried out under relatively lower temp, be at relatively low temperature
It can reach higher degree of graphitization.
Specifically, catalyst two is nickel-base catalyst.Nickel-base catalyst may be such that volatile matter catalytic reforming and generate carbon and receives
Mitron.
Preferably, the heating rate in graphitization reactor and in reforming reactor is 5-10 DEG C/min.
Specifically, it must be to solid sample according to physical method and chemical method that graphite and CNT, which are carried out purifying to refer to,
Purified, specific purification process is then selected according to specific requirement, is not deployed specifically in the present invention.
It should be noted that coal dust is one or more combinations in common lignite, bituminous coal and anthracite, coal dust
Drying process specifically refers to dry 12-48h under the conditions of 105 DEG C in coal.
Compared with prior art, beneficial effects of the present invention are：For coal high temperature graphitization high energy consumption in the prior art and
Fail effectively using the deficiency of volatile matter in graphitizing process, by the way that prepared by catalyzed graphitization and catalytic reforming into CNT
Reaction effectively combines, and prepares graphite under " low temperature ", reduces energy consumption and to effective utilization of fixed carbon in coal, while by urging
Change effective utilization that reforming reaction realizes volatile matter in coal, obtain the CNT of high added value；Both effectively combine, and are realizing
The product of high value is obtained while coal resource cascade utilization, improves the economy of whole technique；Simple production process, pair sets
Standby requirement is not also high, is easy to industrialize.
Brief description of the drawings
Fig. 1 is the schematic diagram of the system of a kind of two-period form co-production coal base graphite provided by the invention and CNT.
In accompanying drawing, the list of parts representated by each label is as follows：
1A. CNT generation modules；1B. graphitization modules；1. waste gas outlet；2. vapor input channel；Under 3-1.
Sieve plate two；3-2. upper sieve plates two；4. reforming reactor；Sieve plate one under 5-1.；5-2. upper sieve plates one；6. current-carrying gas input channel；
7. graphitization reactor；8. intermediate conduit；9. feed inlet and outlet one；10. feed inlet and outlet two；11. catalyst two；12. reaction raw materials.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail, and example is served only for explaining
The present invention, it is not intended to limit the scope of the present invention.
As shown in figure 1, the present invention provides a kind of system of two-period form co-production coal base graphite and CNT, it includes
Graphitization module 1B and CNT generation module 1A, wherein：
The graphitization module 1B includes graphitization reactor 7, is provided with the graphitization reactor 7 at roof upper
The 5-2 of sieve plate one, be provided with the lower 5-1 of sieve plate one at the bottom wall, the roof of the graphitization reactor 7 be provided with sub-export of volatilizing,
Bottom wall is provided with current-carrying gas import, and the side wall of the graphitization reactor 7 is provided with feed inlet and outlet 1；
The CNT generation module 1A includes reforming reactor 4, is provided with the reforming reactor 4 at roof
The 3-2 of upper sieve plate two, the lower 3-1 of sieve plate two is provided with bottom wall, the roof of the reforming reactor 4 is provided with waste gas outlet 1, bottom
Wall is provided with volatile matter import and vapor import, and the side wall of the reforming reactor 4 is provided with feed inlet and outlet 2 10；
The volatilization sub-export is connected with the volatile matter import by intermediate conduit 8, the row of being provided with the waste gas outlet 1
Air valve, the current-carrying gas import connect with current-carrying gas input channel 6, and the vapor import connects with vapor input channel
It is logical, door body able to turn on or off, the graphitization reactor 7 are respectively equipped with the feed inlet and outlet 1 and the feed inlet and outlet 2 10
And electrothermal heating component is respectively equipped with reforming reactor 4.When being produced using said system, placed on the lower 5-1 of sieve plate one
The reaction raw materials 12 formed are mixed with coal dust by catalyst one, catalyst 2 11 is placed with the lower 3-1 of sieve plate two.
It should be noted that upper sieve plate one, lower sieve plate one are by exotic material (corundum etc.), upper sieve plate two and lower sieve plate two
It is made up of exotic material (ceramics or quartz etc.), is densely covered with ventilative sieve aperture thereon, the main function of upper sieve plate is anti-to prevent
Feed particulate material in device is answered to rise with air-flow and flowed out from corresponding reactor, the main function of lower sieve plate is carrying reaction raw materials
And catalyst.Upper and lower sieve plate can be horizontally disposed with, and can be also obliquely installed as needed, to increase area that material can tile or conveniently
Input and output material.Feed inlet and outlet on graphitization reactor and reforming reactor can as shown in fig. 1, and now input and output material passes through reaction
Same opening in device side wall, it is contemplated that special charging can be also separately provided on each reactor as needed
Mouth and special discharging opening.
Further, the intermediate conduit 8 is provided with the air valve to the one-way conduction of reforming reactor 4.
It should be noted that the air valve except there is one-way conduction effect, can also can control keying, the work of stop valve is played
With, when the coal dust fugitive constituent in graphitization reactor through take exercise completely release and with current-carrying gas enter reforming reactor 4 after, can close
Close and state stop valve, there is no energy and mass exchange between two reactors, be easy to each self-reacting temperature control.
Further, the current-carrying gas input channel 6 connects with nitrogen cylinder or other inert gas steel cylinders.
It should be noted that other inert gases can be argon gas, in order to which cost consideration preferably uses nitrogen, current-carrying gas is defeated
Enter and flow control valve is set on pipeline.
Further, the vapor input channel 2 connects with the vapor outlet port of boiler-steam dome.
It should be noted that the temperature of vapor is 100 DEG C, it can be stored in drum with normal pressure or storage of higher pressures, when
It is in order that it is pressed into reforming reactor when normal pressure stores, it should sets booster pump on vapor input channel.
Further, the electrothermal heating component includes heating wire or electric hot plate and the heating wire or electric hot plate are close to described
The lower 5-1 of sieve plate one and lower sieve plate two 3-1 is set.
Following specific embodiment is to be produced using said system progress coal base graphite and CNT, with further
Method provided by the invention is elaborated.
Embodiment 1
A kind of system and method for two-period form co-production coal base graphite and CNT, it mainly comprises the following steps：
S1. take a certain amount of anthracite (Jincheng, Shanxi coal) to be ground by coal pulverizer, 20-40 is sifted out with 20 mesh and 40 mesh sieve
The coal sample of mesh particle diameter, taken out after drying 12h in 105 DEG C of baking ovens；The dried coal sample 20g of 20-40 mesh is taken, adds 2g Fe3O4
Powder (catalyst one) is placed on the lower sieve plate one of graphitization reactor after being sufficiently mixed, while by 1g Ni/Al2O3Catalyst powder
Last (catalyst two) is on the lower sieve plate two of reforming reactor；
S2. the door body closed at the feed inlet and outlet one and feed inlet and outlet two, it is anti-from the import of current-carrying gas to the graphitization
Device is answered to be passed through N2, the air in graphitization reactor and reforming reactor is discharged, continues logical current-carrying gas, it is anti-that graphitization is respectively started
The electrothermal heating component in device and reforming reactor is answered, when graphitization reactor is warming up to 900 DEG C (8 DEG C of heating rate/
Min), the temperature of reforming reactor is about 562 DEG C (5 DEG C/min of heating rate), now closes waste gas outlet and is entered by vapor
Mouth is passed through vapor into the reforming reactor, stops being passed through vapor after 15min, while stop being passed through N2, the water that is passed through
The gross mass of steam is 6g；
S3. 1500 DEG C are continuously heating to and is maintained since when its temperature rises to 900 DEG C in the graphitization reactor
(about 75min, 8 DEG C/min of heating rate), 1500 DEG C are maintained to continue to react 1.5h, herein the temperature in interior reforming reactor therebetween
Control as 650-750 DEG C, since being passed through vapor, reforming reaction continues 2h, and reaction is down to normal temperature after terminating, and then opens useless
Gas exiting exhaust gas, the product on the product and lower sieve plate two on lower sieve plate one, warp are taken out through feed inlet and outlet one and feed inlet and outlet two
Coal base graphite and CNT are respectively obtained after purification.
To take out product (not purifying) from graphitization reactor as sample one, via XRD (X-ray diffraction) detections point
Analysis, calculates its degree of graphitization.Product (not purifying) to be taken out from reforming reactor (scans electricity for sample two via SEM
Mirror) and TEM (transmission electron microscope) analyses, analyze its pattern form.Testing result shows, the graphitization of sample one in the implementation case
Degree has reached more than 80%, is not added with Fe3O4When, the degree of graphitization 15% of sample is obtained under equal conditions, and sample two is in the secure execution mode (sem
A large amount of CNT generations can clearly be observed.
Embodiment 2
A kind of system and method for two-period form co-production coal base graphite and CNT, it mainly comprises the following steps：
S1. take a certain amount of anthracite (Jincheng, Shanxi coal) to be ground by coal pulverizer, 20-40 is sifted out with 20 mesh and 40 mesh sieve
The coal sample of mesh particle diameter, taken out after drying 12h in 105 DEG C of baking ovens；The dried coal sample 20g of 20-40 mesh is taken, adds 1g Fe2O3
Powder (catalyst one) is placed on the lower sieve plate one of graphitization reactor after being sufficiently mixed, while by 1g Ni/Al2O3Catalyst powder
Last (catalyst two) is on the lower sieve plate two of reforming reactor；
S2. the door body closed at the feed inlet and outlet one and feed inlet and outlet two, it is anti-from the import of current-carrying gas to the graphitization
Device is answered to be passed through N2, the air in graphitization reactor and reforming reactor is discharged, continues logical current-carrying gas, it is anti-that graphitization is respectively started
The electrothermal heating component in device and reforming reactor is answered, when graphitization reactor is warming up to 900 DEG C (8 DEG C of heating rate/
Min), the temperature of reforming reactor is about 675 DEG C (6 DEG C/min of heating rate), now closes waste gas outlet and is entered by vapor
Mouth is passed through vapor into the reforming reactor, stops being passed through vapor after 12min, while stop being passed through N2, the water that is passed through
The gross mass of steam is 4g；
S3. 1380 DEG C are continuously heating to and is maintained since when its temperature rises to 900 DEG C in the graphitization reactor
(about 60min, 8 DEG C/min of heating rate), 1380 DEG C are maintained to continue to react 2h, herein the temperature control in interior reforming reactor therebetween
750-900 DEG C is made as, since being passed through vapor, reforming reaction continues 2h, and reaction is down to normal temperature after terminating, then opens waste gas
Exiting exhaust gas, the product on the product and lower sieve plate two on lower sieve plate one is taken out through feed inlet and outlet one and feed inlet and outlet two, through pure
Coal base graphite and CNT are respectively obtained after change.
To take out product (not purifying) from graphitization reactor as sample one, via XRD (X-ray diffraction) detections point
Analysis, calculates its degree of graphitization.Product (not purifying) to be taken out from reforming reactor (scans electricity for sample two via SEM
Mirror) and TEM (transmission electron microscope) analyses, analyze its pattern form.Testing result shows, the graphitization of sample one in the implementation case
Degree has reached more than 75%, is not added with Fe2O3When, the degree of graphitization 15% of sample is obtained under equal conditions, and sample two is in the secure execution mode (sem
A large amount of CNT generations can clearly be observed.
Embodiment 3
A kind of system and method for two-period form co-production coal base graphite and CNT, it mainly comprises the following steps：
S1. take a certain amount of anthracite (Jincheng, Shanxi coal) to be ground by coal pulverizer, 20-40 is sifted out with 20 mesh and 40 mesh sieve
The coal sample of mesh particle diameter, taken out after drying 12h in 105 DEG C of baking ovens；The dried coal sample 20g of 20-40 mesh is taken, adds 4g iron powders
(catalyst one) is placed in after being sufficiently mixed on the lower sieve plate one of graphitization reactor, while by 3g Ni/Al2O3Catalyst fines
(catalyst two) is on the lower sieve plate two of reforming reactor；
S2. the door body closed at the feed inlet and outlet one and feed inlet and outlet two, it is anti-from the import of current-carrying gas to the graphitization
Device is answered to be passed through N2, the air in graphitization reactor and reforming reactor is discharged, continues logical current-carrying gas, it is anti-that graphitization is respectively started
The electrothermal heating component in device and reforming reactor is answered, when graphitization reactor is warming up to 900 DEG C (8 DEG C of heating rate/
Min), the temperature of reforming reactor is about 900 DEG C (8 DEG C/min of heating rate), now closes waste gas outlet and is entered by vapor
Mouth is passed through vapor into the reforming reactor, stops being passed through vapor after 12min, while stop being passed through N2, the water that is passed through
The gross mass of steam is 4g；
S3. 1580 DEG C are continuously heating to and is maintained since when its temperature rises to 900 DEG C in the graphitization reactor
(about 85min, 8 DEG C/min of heating rate), 1580 DEG C are maintained to continue to react 2h, herein the temperature control in interior reforming reactor therebetween
900 DEG C are made as, since being passed through vapor, reforming reaction continues 2h, and reaction is down to normal temperature after terminating, then opens waste gas outlet
Exhaust, the product on the product and lower sieve plate two on lower sieve plate one is taken out through feed inlet and outlet one and feed inlet and outlet two, after purified
Respectively obtain coal base graphite and CNT.
To take out product (not purifying) from graphitization reactor as sample one, via XRD (X-ray diffraction) detections point
Analysis, calculates its degree of graphitization.Product (not purifying) to be taken out from reforming reactor (scans electricity for sample two via SEM
Mirror) and TEM (transmission electron microscope) analyses, analyze its pattern form.Testing result shows, the graphitization of sample one in the implementation case
Degree has reached more than 85%, the degree of graphitization 15% of sample is obtained when being not added with iron powder, under equal conditions, sample two is in the secure execution mode (sem
A large amount of CNT generations can clearly be observed.
As seen from the above embodiment, the carry out cascade utilization that system and method provided by the invention can be to coal resource, it is real
The coproduction of coal base graphite and CNT is showed.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
1. the system of a kind of two-period form co-production coal base graphite and CNT, it is characterised in that including graphitization module
(1B) and CNT generation module (1A), wherein：
The graphitization module (1B) includes graphitization reactor (7), is provided with the graphitization reactor (7) at roof
Upper sieve plate one (5-2), lower sieve plate one (5-1) is provided with bottom wall, the roof of the graphitization reactor (7) is provided with volatilization
Sub-export, bottom wall are provided with current-carrying gas import, and the side wall of the graphitization reactor (7) is provided with feed inlet and outlet one (9), described
Feed inlet and outlet one (9) is located at the top of the lower sieve plate one (5-1)；
The CNT generation module (1A) includes reforming reactor (4), is set in the reforming reactor (4) at roof
There is upper sieve plate two (3-2), be provided with lower sieve plate two (3-1) at bottom wall, the roof of the reforming reactor (4) is provided with waste gas
Outlet (1), bottom wall are provided with volatile matter import and vapor import, and the side wall of the reforming reactor (4) is provided with input and output material
Two (10) of mouth, the feed inlet and outlet two (10) are located at the top of the lower sieve plate two (3-1)；
The volatilization sub-export is connected with the volatile matter import by intermediate conduit (8), and waste gas outlet (1) place is provided with row
Air valve, the current-carrying gas import connect with current-carrying gas input channel (6), and the vapor import connects with vapor input channel
Logical, the feed inlet and outlet one (9) and the feed inlet and outlet two (10) place are respectively equipped with door body able to turn on or off, the graphitization reaction
Electrothermal heating component is respectively equipped with device (7) and reforming reactor (4).
2. the system of a kind of two-period form co-production coal base graphite according to claim 1 and CNT, its feature exist
In the intermediate conduit (8) is provided with the check valve to the reforming reactor (4) one-way conduction.
3. the system of a kind of two-period form co-production coal base graphite according to claim 1 and CNT, its feature exist
In the current-carrying gas input channel (6) connects with nitrogen cylinder or other inert gas steel cylinders.
4. the system of a kind of two-period form co-production coal base graphite according to claim 1 and CNT, its feature exist
In the vapor input channel (2) connects with the vapor outlet port of boiler-steam dome.
5. the system of a kind of the two-period form co-production coal base graphite and CNT according to any one of Claims 1-4,
Characterized in that, the electrothermal heating component includes heating wire or electric hot plate and the heating wire or electric hot plate are close to the lower sieve
Plate one (5-1) and lower sieve plate two (3-1) are set.
6. a kind of method of two-period form co-production coal base graphite and CNT, it is characterised in that utilize claim 1 to 5
System described in any one is produced, and is comprised the following steps：
S1. by coal dust and catalyst one according to 5-20:1 mass ratio is sufficiently mixed to obtain reaction raw materials (12), reaction raw materials
(12) added by feed inlet and outlet one (9) in the graphitization reactor (7), while from feed inlet and outlet two (10) to the reformation
The mass ratio of addition catalyst two (11) in reactor (4), coal dust and catalyst two is 5-20:1；
S2. the door body at the feed inlet and outlet one (9) and feed inlet and outlet two (10) place is closed, from the import of current-carrying gas to the graphitization
Reactor (7) is passed through current-carrying gas, discharges the air in graphitization reactor (7) and reforming reactor (4), continues logical current-carrying gas,
The electrothermal heating component in graphitization reactor (7) and reforming reactor (4) is respectively started, when graphitization reactor (7) heats up
During to 900 DEG C, the temperature control of reforming reactor (4) is 550-900 DEG C, now closes waste gas outlet (1) and is entered by vapor
Mouth is passed through vapor into the reforming reactor (4), stops being passed through vapor after 10-15min, while stop being passed through current-carrying
Gas, the gross mass for the vapor being passed through are the 5-30% of quality of pc；
S3. in the graphitization reactor (7) since when its temperature rises to 900 DEG C, it is 900-1600 DEG C to maintain its interior temperature,
1-3h is reacted, the temperature control in interior reforming reactor (4) is 550-900 DEG C therebetween herein, since being passed through vapor, is reformed
Reaction continues 1-3h, and reaction is down to normal temperature after terminating, and the drain tap for then opening waste gas outlet (1) place is exhausted, through entering
Discharging opening one (9) and feed inlet and outlet two (10) take out the product on product and lower sieve plate two (3-1) on lower sieve plate one (5-1),
Coal base graphite and CNT are respectively obtained after purified.
7. the method for a kind of two-period form co-production coal base graphite according to claim 6 and CNT, its feature exist
In coal dust, catalyst one and catalyst two (11) by grinding and drying process, coal dust, catalyst one and are urged before addition
Particle diameter after agent two (11) grinding is 20-100 mesh.
8. the method for a kind of two-period form co-production coal base graphite according to claim 6 and CNT, its feature exist
It is one or more mixed in the simple substance, oxide and chloride that, catalyst one is Fe, Ni, Mn, Mg, Zn, Ca, W, Cu and B
Close.
9. the method for a kind of two-period form co-production coal base graphite according to claim 6 and CNT, its feature exist
In catalyst two (11) is nickel-base catalyst.
10. the side of a kind of the two-period form co-production coal base graphite and CNT according to any one of claim 6 to 9
Method, it is characterised in that the heating rate in graphitization reactor (7) and in reforming reactor (4) is 5-10 DEG C/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746059A (en) * | 2017-09-15 | 2018-03-02 | 武汉理工大学 | A kind of preparation method of the hollow silica microsphere of surface silane-containing modification |
| CN110562960A (en) * | 2019-09-05 | 2019-12-13 | 太原理工大学 | preparation and purification method of coal-based carbon nano tube |
| CN110713179A (en) * | 2019-10-10 | 2020-01-21 | 太原理工大学 | Coal-based carbon nanotube for deoxidizing low-concentration coal bed gas and preparation and purification methods thereof |
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| CN103288076A (en) * | 2013-06-08 | 2013-09-11 | 新疆师范大学 | Method for preparing multilayer graphene from coal-base raw material |
| CN105819430A (en) * | 2016-03-16 | 2016-08-03 | 中国科学院山西煤炭化学研究所 | Preparation method of coal base graphene |
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| CN103288076A (en) * | 2013-06-08 | 2013-09-11 | 新疆师范大学 | Method for preparing multilayer graphene from coal-base raw material |
| CN105819430A (en) * | 2016-03-16 | 2016-08-03 | 中国科学院山西煤炭化学研究所 | Preparation method of coal base graphene |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746059A (en) * | 2017-09-15 | 2018-03-02 | 武汉理工大学 | A kind of preparation method of the hollow silica microsphere of surface silane-containing modification |
| CN107746059B (en) * | 2017-09-15 | 2020-01-14 | 武汉理工大学 | Preparation method of hollow silica microspheres with silane-modified surfaces |
| CN110562960A (en) * | 2019-09-05 | 2019-12-13 | 太原理工大学 | preparation and purification method of coal-based carbon nano tube |
| CN110562960B (en) * | 2019-09-05 | 2022-08-02 | 太原理工大学 | Preparation and purification method of coal-based carbon nano tube |
| CN110713179A (en) * | 2019-10-10 | 2020-01-21 | 太原理工大学 | Coal-based carbon nanotube for deoxidizing low-concentration coal bed gas and preparation and purification methods thereof |
| CN110713179B (en) * | 2019-10-10 | 2023-02-28 | 太原理工大学 | Coal-based carbon nano tube for deoxidizing low-concentration coal bed gas and preparation and purification methods thereof |
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