CN107720747A - A kind of preparation method rich in mesopore asphalt-base globular active carbon - Google Patents
A kind of preparation method rich in mesopore asphalt-base globular active carbon Download PDFInfo
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Abstract
A kind of preparation method rich in mesopore asphalt-base globular active carbon is that asphalt stock and Lewis acid catalyst compounds are worn into micro mist, then directly sealing is warming up to reaction temperature in input autoclave, stirring, isothermal reaction obtains the pitch of the interphase containing part, ground, it is ultrasonically treated in organic solvent, it is then poured into reactor, add surface active agent polyvinyl alcohol and water, suspend balling-up after stirring heating, carry out steam activation is not melted into ball warp oxidation, produced rich in mesopore asphalt-base globular active carbon.The present invention have method it is simple, without any additive, the advantages of specific surface area is high, and thermal conductivity is good, and mesopore content is more.
Description
Technical field
The invention belongs to the preparation field of spheric active carbon, and in particular to a kind of rich in mesopore asphalt-base globular active carbon
Preparation method.
Background technology
Spheric active carbon has big specific surface area height, pore volume, heap density height, good biocompatibility, hydrodynamic performance good
Etc. a series of good characteristics so that it has been widely used in the fields such as catalyst carrier, adsorbent, pharmaceutical carrier tool.
Pitch has the advantages that phosphorus content height, good fluidity, is easy to graphitization, has fabulous compatibility with carbonaceous aggregate,
Usually as the presoma of spheric active carbon.Pitch, organo-metallic compound and aromatic solvent are pressed in patent CN1224034A
Certain proportion mixes in autoclave high temperature, the asphalt stock of metal-particle-containing is made, through emulsion process balling-up.Patent
CN102795624A by benzoyl peroxide, divinylbenzene, styrene, diethylbenzene and softening point be 240~280 DEG C and particle diameter
For the asphalt powder batch mixing of 150~200 mesh sieves, suspend balling-up in polyvinyl alcohol dispersion liquid.Above patent, balling technique is complicated,
Comparatively dense, macropore in shortage inside prepared bitumen ball.It is unfavorable for the diffusion of oxygen when oxidation is not melted, adds steady
Surely time and energy consumption are changed, moreover, being also unfavorable for the progress of its later stage activation process.
Traditionally, for asphalt-base globular active carbon based on micropore, middle macropore ratio is less, limit its liquid phase adsorption,
The application of the occasions such as Industrial Catalysis.To prepare the spheric active carbon rich in mesopore, patent CN1250024A will once activate obtained
Asphalt-base globular active carbon in the solution of different metal compound time of infusion, dry after, enter at 900 DEG C water-filling steaming
Gas re-activation.Pitch ball warp re-activation in the inventive method, add production cycle and energy consumption of reaction, and prepared production
Big porosity is still relatively low in product.In addition, patent CN103787331A is using mesophase pitch as raw material, it is fragrant by adding first
The additive such as hydrocarbons and thermosetting phenolic resin is modulated to it, and modulation products prepares bitumen ball through suspension method, most
Asphalt-base spherical activated carbon is prepared using techniques such as conventional pre-oxidation, charing and activation afterwards.Although produced obtained by the inventive method
The mesoporous rate of product is higher, but need to add additive and pitch is modulated, and because molecular polarity differs greatly, causes pitch with adding
Add " miscible " degree of agent poor, and can the pore structure that this point is directly connected to final products uniformly develop.In addition, the work
Skill complex operation.
Patent CN106348290A is prepared for a kind of high-termal conductivity asphalt-base globular active carbon, and the process needs to add heat conduction
Agent such as one or both of mesophase pitch powder, mesophase asphalt carbon fiber, graphite powder, graphite worm mixture.The invention
Although the preferable spheric active carbon of thermal conductivity can be made in method, the introducing of thermal conducting agent adds production cost, thereby increases and it is possible to deposits
Disperseing the problem of uneven, the pore structure of the spheric active carbon prepared by this kind of method is still based on micropore.Existing document table
Bright, the carbonized product of mesophase pitch has the characteristics that electrical and thermal conductivity is good, high intensity.Therefore, for reference to isotropic pitch
With the advantage of mesophase pitch between the two, using the pitch of the interphase containing part as raw material, or product of high quality and at a reasonable price can be prepared,
But rarely has Patents report.
The content of the invention
For it is current the shortcomings that, it is an object of the invention to provide a kind of method it is simple, without any additive, specific surface area
Height, the method that the spheric active carbon rich in mesopore is prepared using pitch as raw material more than mesopore content.
The isotropic pitch of the interphase containing part is made in the present invention first, and the asphalt powder is ultrasonic in organic solvent
It is scattered, it is subsequently transferred to add suitable quantity of water and polyvinyl alcohol in reactor, stirring heating suspension balling-up.When organic solvent volatilizees
Afterwards, mesopore under bitumen ball internal reservation.The ball warp oxidation do not melt and then through steam activation promote its micropore generation and
Further reaming.
The preparation method of the present invention comprises the following steps：
Asphalt stock and Lewis acid catalyst compounds are worn into 80-200 mesh micro mists, then put into autoclave
Directly sealing is warming up to 250-400 DEG C of reaction temperature, stirs, isothermal reaction 1-4h obtains the pitch of the interphase containing part, by it
Grind, be sieved into 10-100 mesh powder, ultrasonic 10-100min, is then poured into reactor in organic solvent, adds surface and lives
Property agent polyethylene alcohol and water, stirring be warming up to 100-150 DEG C of suspension balling-up.At 750-950 DEG C after ball warp oxidation is not melted
Lower progress steam activation 0.5-3h, is produced rich in mesopore asphalt-base globular active carbon.
As described above, asphalt stock includes one or more of mixtures in asphalt, coal tar pitch, bitumen.
As described above, Lewis acid catalysts are anhydrous AlCl3, anhydrous FeCl3, anhydrous CoCl2、BF3In one kind or several
Kind of mixture, and it is 0.5-5%, preferably 2-4% that addition, which accounts for the weight fraction of material asphalt,.
As described above, pitch is ground into micro mist with Lewis acid catalyst compounds, compound reaction temperature is preferably 300-
350℃。
As described above, organic solvent includes the one or more in methanol, ethanol, ethylene glycol and acetone, and added
Solvent and the weight ratio containing mesophase pitch powder are 0.5-3, preferably 1.5-2.
As described above, the addition of surface active agent polyvinyl alcohol and water is polyvinyl alcohol：Water：Containing mesophase pitch powder
Weight ratio be 2.5-50：500-1000：10.Preferably 10-30：600-800：10.
The inventive method difference with the prior art is：Worn into after asphalt stock is mixed with Lewis acid catalysts micro-
Powder, be advantageous to fully contact between material, improve catalytic effect, reduce catalyst amount.The present invention is complete in autoclave
Into, it is not necessary to nitrogen is passed through in advance, and uses the shorter reaction time, reduces energy consumption and the requirement to equipment.It is prior
It is that this method can ensure that generated part interphase exists in the matrix of isotropic pitch with mosaic texture, in avoiding
Between phase bead largely it is molten simultaneously, generate domain type interphase.The present invention is before suspension method prepares bitumen ball, first by material organic molten
Ultrasonic disperse in agent.Operation is simple for this so that organic solvent is easily diffused to inside pitch particle, is volatilized for later stage solvent
And leave middle macropore and provide possibility.If without this operation, middle macropore, specific difference detailed in Example can not be obtained.
In addition, advantage of the invention is that：Pitch is pre-formed middle macropore, advantageously reduced during ball is synthesized
Water vapor diffusion resistance and shorten diffusion length, promote the development of pore structure so that bitumen ball lower temperature and it is shorter when
Interior to complete to activate, macropore ratio is higher in prepared spheric active carbon.In addition, part interphase drips in isotropism
Blue or green situ generation, and be uniformly distributed.And the asphalt-base globular active carbon prepared using this pitch as raw material, may have good
Electrical and thermal conductivity, extend its application potential.
The specific surface area of gained activated carbon of the invention is 825.1m2/g-1325.9m2/ g, mesoporous 37.3%-
47.7%, the specific surface area 372.9m of the activated carbon prepared far above conventional method in comparative example2/g-731.2m2/ g and mesopore
Rate 7.5%-17.3%.
Embodiment
The inventive method will be further described by some embodiments below.
Embodiment 1
By 200g coal tar pitch and the anhydrous AlCl of 4g3Mixing, is ground into 200 mesh powder, puts into autoclave and mix
400 DEG C are uniformly heating to, constant temperature 4h obtains the pitch of the interphase containing part, and now, the content of interphase is 22.9wt%.By its
It is ground into 60 mesh powders.Wherein 20g powder is taken, ultrasonic 30min, is then poured into reactor in 10g ethanol, adds
2000ml water and 100g polyvinyl alcohol, stirring are warming up to 150 DEG C, obtain bitumen ball.After ball warp oxidation is not melted at 800 DEG C
Steam activation 1h is carried out, is produced rich in mesopore asphalt-base globular active carbon, the surface area of activated carbon is 875.1m2/ g, mesopore
Rate is 38.3%.
Comparative example 1
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 625.1m2/ g, mesoporous 12.3%.
Embodiment 2
By 200g bitumens and the anhydrous FeCl of 8g3Mixing, is ground into 120 mesh powder, puts into autoclave and stir
Mix and be uniformly heating to 300 DEG C, constant temperature 3h obtains the pitch of the interphase containing part, and now, the content of interphase is 25.5wt%.Will
It grinds, is sieved into 20 mesh powders.Wherein 20g powder is taken, (both weight are than 1 in 40g ethanol and ethylene glycol:2) mix molten
Ultrasonic 10min, is then poured into reactor in agent, adds 1200ml water and 30g polyvinyl alcohol, and stirring is warming up to 110 DEG C.Should
Ball warp oxidation carries out steam activation 1.5h after not melting at 850 DEG C, produces rich in mesopore asphalt-base globular active carbon, activity
The surface area of charcoal is 835.4m2/ g, mesoporous 37.3%.
Comparative example 2
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 572.8m2/ g, mesoporous 9.3%.
Embodiment 3
By 200g asphalt and the anhydrous CoCl of 10g2Mixing, is ground into 80 mesh powder, puts into autoclave and stir
Mix and be uniformly heating to 350 DEG C, constant temperature 4h obtains the pitch of the interphase containing part, and now, the content of interphase is 37.3wt%.Will
It grinds, is sieved into 20 mesh powders.Wherein 20g powder is taken, ultrasonic 60min, is then poured into reactor in 30g methanol solvates
In, 1000ml water, 5g polyvinyl alcohol are added, stirring is warming up to 150 DEG C.Carried out after ball warp oxidation is not melted at 750 DEG C
Steam activation 0.5h, produce rich in mesopore asphalt-base globular active carbon, the surface area of activated carbon is 885.1m2/ g, mesoporous
For 43.7%.
Comparative example 3
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 395.1m2/ g, mesoporous 9.1%.
Embodiment 4
By 200g coal tar pitch and the anhydrous CoCl of 2g2Mixing, is ground into 80 mesh powder, puts into autoclave and stirs
Even to be warming up to 320 DEG C, constant temperature 3h obtains the pitch of the interphase containing part, and now, the content of interphase is 19.3wt%.Ground
Grind, be sieved into 20 mesh powders.Wherein 20g powder is taken, ultrasonic 60min, is then poured into reactor in 30g ethylene glycol solvents
In, 1600ml water, 60g polyvinyl alcohol are added, stirring is warming up to 150 DEG C.Carried out after ball warp oxidation is not melted at 800 DEG C
Steam activation 0.5h, produce rich in mesopore asphalt-base globular active carbon, the surface area of activated carbon is 1325.9m2/ g, mesoporous
For 47.7%.
Comparative example 4
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 715.3m2/ g, mesoporous 14.1%.
Embodiment 5
By 200g asphalt and the anhydrous AlCl of 1g3Mixing, is ground into 140 mesh powder, puts into autoclave and stir
Mix and be uniformly heating to 300 DEG C, constant temperature 2h obtains the pitch of the interphase containing part, and now, the content of interphase is 15.3wt%.Will
It grinds, is sieved into 20 mesh powders.Wherein 20g powder is taken, ultrasonic 60min, is then poured into reactor in 30g methanol solvates
In, 1600ml water, 20g polyvinyl alcohol are added, stirring is warming up to 150 DEG C.Carried out after ball warp oxidation is not melted at 750 DEG C
Steam activation 0.5h, produce rich in mesopore asphalt-base globular active carbon, the surface area of activated carbon is 990.0m2/ g, mesoporous
For 41.6%.
Comparative example 5
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 731.2m2/ g, mesoporous 17.3%.
Embodiment 6
By 200g asphalt and the anhydrous FeCl of 4g3Mixing, is ground into 80 mesh powder, puts into autoclave and stir
350 DEG C are uniformly heating to, constant temperature 4h obtains the pitch of the interphase containing part, and now, the content of interphase is 31.1wt%.By its
Grind, be sieved into 20 mesh powders.Wherein 20g powder is taken, ultrasonic 60min, is then poured into reactor in 30g acetone solvents
In, 1800ml water, 40g polyvinyl alcohol are added, stirring is warming up to 150 DEG C.Carried out after ball warp oxidation is not melted at 750 DEG C
Steam activation 0.5h, produce rich in mesopore asphalt-base globular active carbon, the surface area of activated carbon is 825.7m2/ g, mesoporous
For 45.7%.
Comparative example 6
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 479.9m2/ g, mesoporous 9.1%.
Embodiment 7
By the mixture of 200g coal tar pitch and asphalt, (both weight are than 1:3) with 6g BF3Mixing, is ground into 100 mesh
Powder, puts into autoclave to stir and is warming up to 250 DEG C, and constant temperature 2h obtains the pitch of the interphase containing part, now,
The content of interphase is 22.7wt%.Ground, be sieved into 60 mesh powders.Wherein 20g powder is taken, in 60g acetone solvents
Middle ultrasonic 100min, is then poured into reactor, adds 1500ml water and 50g polyvinyl alcohol, and stirring is warming up to 120 DEG C.Should
Ball warp oxidation carries out steam activation 3h after not melting at 750 DEG C, produces rich in mesopore asphalt-base globular active carbon, activated carbon
Surface area be 935.4m2/ g, mesoporous 43.1%.
Comparative example 7
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 674.8m2/ g, mesoporous 13.4%.
Embodiment 8
By the mixture of 200g coal tar pitch and asphalt, (both weight are than 1:1) with 8g AlCl3Mixing, is ground into 140
Mesh powder, puts into autoclave to stir and is warming up to 280 DEG C, and constant temperature 2h obtains the pitch of the interphase containing part, this
When, the content of interphase is 32.7wt%.Ground, be sieved into 60 mesh powders.Wherein 20g powder is taken, it is molten in 60g methanol
Ultrasonic 100min, is then poured into reactor in agent, adds 1600ml water and 60g polyvinyl alcohol, and stirring is warming up to 120 DEG C.Will
Ball warp oxidation carries out steam activation 1h after not melting at 950 DEG C, produces rich in mesopore asphalt-base globular active carbon, activity
The surface area of charcoal is 986.4m2/ g, mesoporous 45.8%.
Comparative example 8
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 520.8m2/ g, mesoporous 8.0%.
Embodiment 9
By 200g coal tar pitch and the anhydrous AlCl of 3g3With anhydrous FeCl3Mixture (both weight are than 1:2) 120, are ground into
Mesh powder, puts into autoclave to stir and is warming up to 360 DEG C, and constant temperature 1h obtains the pitch of the interphase containing part, this
When, the content of interphase is 25.9wt%.Ground, be sieved into 60 mesh powders.Wherein 20g powder is taken, it is molten in 60g acetone
Ultrasonic 100min, is then poured into reactor in agent, adds 1200ml water and 25g polyvinyl alcohol, and stirring is warming up to 120 DEG C.Will
Ball warp oxidation carries out steam activation 2.5h after not melting at 750 DEG C, produces rich in mesopore asphalt-base globular active carbon, living
The surface area of property charcoal is 950.4m2/ g, mesoporous 44.6%.
Comparative example 9
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 601.2m2/ g, mesoporous 9.1%.
Embodiment 10
By the mixture of 200g coal tar pitch and bitumen, (both weight are than 1:1) with the anhydrous AlCl of 3g3With anhydrous FeCl3
Mixture (both weight are than 1:2) 80 mesh powder, are ground into, puts into autoclave to stir and is warming up to 300 DEG C,
Constant temperature 4h obtains the pitch of the interphase containing part, and now, the content of interphase is 20.2wt%.Ground, be sieved into 10 mesh
Powder.Wherein 20g powder is taken, (three's weight is than 1 in the mixed solvent of 20g methanol, ethanol, ethylene glycol:2:1) it is ultrasonic in
20min, it is then poured into reactor, adds 1200ml water and 50g polyvinyl alcohol, stirring is warming up to 100 DEG C.The ball warp is aoxidized
Steam activation 0.5h is carried out after not melting at 950 DEG C, is produced rich in mesopore asphalt-base globular active carbon, the surface of activated carbon
Product is 1124.4m2/ g, mesoporous 42.1%.
Comparative example 10
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 690.3m2/ g, mesoporous 14.3%.
Embodiment 11
By 200g selected from coal tar pitch and petroleum asphalt and natural mixture of asphalt, (three's weight is than 1:1:1) with the anhydrous AlCl of 3g3With
Anhydrous CoCl2Mixture (both weight are than 2:1) 140 mesh powder, are ground into, put into autoclave the liter that stirs
Temperature is to 330 DEG C, and constant temperature 3h obtains the pitch of the interphase containing part, and now, the content of interphase is 27.2wt%.Ground,
It is sieved into 50 mesh powders.Wherein 20g powder is taken, (three's weight is than 1 in the mixed solvent of 30g methanol, ethanol, acetone:1:1)
Middle ultrasonic 70min, is then poured into reactor, adds 1500ml water and 45g polyvinyl alcohol, and stirring is warming up to 130 DEG C.By the ball
It is oxidized do not melt after at 850 DEG C carry out steam activation 1h, produce rich in mesopore asphalt-base globular active carbon, activated carbon
Surface area is 927.6m2/ g, mesoporous 41.6%.
Comparative example 11
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 524.1m2/ g, mesoporous 8.8%.
Embodiment 12
By 200g asphalt and natural mixture of asphalt, (the two weight is than 1:3) with the anhydrous FeCl of 8g3And BF3Mixing
(both weight are than 1 for thing:1) 170 mesh powder, are ground into, puts into autoclave to stir and is warming up to 360 DEG C, constant temperature
1h obtains the pitch of the interphase containing part, and now, the content of interphase is 36.2wt%.Ground, be sieved into the powder of 40 mesh
End.Wherein 20g powder is taken, (the two weight is than 2 in the mixed solvent of 30g methanol, acetone:1) ultrasonic 80min, is then poured into
In reactor, 1500ml water and 90g polyvinyl alcohol are added, stirring is warming up to 150 DEG C.800 after ball warp oxidation is not melted
Steam activation 2.5h is carried out at DEG C, is produced rich in mesopore asphalt-base globular active carbon, the surface area of activated carbon is 897.6m2/
G, mesoporous 42.7%.
Comparative example 12
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 422.6m2/ g, mesoporous 8.3%.
Embodiment 13
By 200g selected from coal tar pitch and petroleum asphalt and natural mixture of asphalt, (three's weight is than 3:1:1) with the anhydrous AlCl of 6g3、
FeCl3And CoCl2Mixture (three's weight is than 1:1:1) 140 mesh powder, are ground into, puts into autoclave and stirs
Even to be warming up to 350 DEG C, constant temperature 3h obtains the pitch of the interphase containing part, and now, the content of interphase is 39.2wt%.Ground
Grind, be sieved into 100 mesh powders.Wherein 20g powder is taken, (the two weight is than 4 in the mixed solvent of 30g methanol, ethanol:1) in
Ultrasonic 90min, is then poured into reactor, adds 1500ml water and 75g polyvinyl alcohol, and stirring is warming up to 150 DEG C.By the ball warp
Oxidation carries out steam activation 2h after not melting at 850 DEG C, produces rich in mesopore asphalt-base globular active carbon, the table of activated carbon
Area is 987.8m2/ g, mesoporous 42.6%.
Comparative example 13
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 372.9m2/ g, mesoporous 7.5%.
Embodiment 14
By 200g selected from coal tar pitch and petroleum asphalt and natural mixture of asphalt, (three's weight is than 1:2:2) with the anhydrous AlCl of 4g3、
FeCl3And CoCl2Mixture (three's weight is than 1:1:2) 100 mesh powder, are ground into, puts into autoclave and stirs
Even to be warming up to 300 DEG C, constant temperature 2.5h obtains the pitch of the interphase containing part, and now, the content of interphase is 29.2wt%.By its
Grind, be sieved into 100 mesh powders.Wherein 20g powder is taken, (the two weight is than 4 in the mixed solvent of 30g methanol, acetone:1)
Middle ultrasonic 90min, is then poured into reactor, adds 1600ml water and 60g polyvinyl alcohol, and stirring is warming up to 150 DEG C.By the ball
It is oxidized do not melt after at 830 DEG C carry out steam activation 2h, produce rich in mesopore asphalt-base globular active carbon, activated carbon
Surface area is 1027.8m2/ g, mesoporous 44.5%.
Comparative example 14
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 685.7m2/ g, mesoporous 12.8%.
Embodiment 15
By 210g selected from coal tar pitch and petroleum asphalt and natural mixture of asphalt, (three's weight is than 1:1:1) with the anhydrous AlCl of 8g3、
FeCl3、CoCl2And BF3Mixture (four weight are than 1:1:1:1) 100 mesh powder, are ground into, are put into autoclave
Stir and be warming up to 300 DEG C, constant temperature 3h obtains the pitch of the interphase containing part, and now, the content of interphase is 24.2wt%.
Ground, be sieved into 100 mesh powders.Take wherein 20g powder, 30g methanol, ethanol, acetone mixed solvent (three weight
Measure ratio 1:1:1) ultrasonic 90min, is then poured into reactor in, adds 2000ml water and 80g polyvinyl alcohol, stirring are warming up to
150℃.Steam activation 1.5h is carried out at 780 DEG C after ball warp oxidation is not melted, is produced rich in mesopore asphalt-base globular
Activated carbon, the surface area of activated carbon is 897.8m2/ g, mesoporous 42.9%.
Comparative example 15
Mesophase pitch is contained using above-mentioned same batch, without the scattered ultrasound of solvent, directly suspend balling-up, keep dispensing and
Subsequent technique condition is constant, and the surface area of obtained asphalt-base globular active carbon is 630.6m2/ g, mesoporous 8.5%.
Claims (9)
1. a kind of preparation method rich in mesopore asphalt-base globular active carbon, it is characterised in that comprise the following steps：
Asphalt stock and Lewis acid catalyst compounds are worn into 80-200 mesh micro mists, then put into autoclave directly
Sealing is warming up to 250-400 DEG C of reaction temperature, stirs, and isothermal reaction 1-4h obtains the pitch of the interphase containing part, ground,
10-100 mesh powder is sieved into, ultrasonic 10-100 min, are then poured into reactor in organic solvent, add surfactant
Polyethylene alcohol and water, stirring are warming up to 100-150 DEG C of suspension balling-up；Enter after ball warp oxidation is not melted at 750-950 DEG C
Water-filling steam activation 0.5-3h, is produced rich in mesopore asphalt-base globular active carbon.
2. a kind of preparation method rich in mesopore asphalt-base globular active carbon as claimed in claim 1, it is characterised in that described
Asphalt stock includes one or more of mixtures in asphalt, coal tar pitch, bitumen.
3. a kind of preparation method rich in mesopore asphalt-base globular active carbon as claimed in claim 1, it is characterised in that described
Lewis acid catalysts are anhydrous AlCl3, anhydrous FeCl3, anhydrous CoCl2、BF3In one or more of mixtures, and addition
The weight fraction for accounting for material asphalt is 0.5-5%.
A kind of 4. preparation method rich in mesopore asphalt-base globular active carbon as claimed in claim 3, it is characterised in that Lewis
The weight fraction that acid catalyst addition accounts for material asphalt is 2-4%.
5. a kind of preparation method rich in mesopore asphalt-base globular active carbon as claimed in claim 1, it is characterised in that described
The reaction temperature of pitch and Lewis acid catalyst compounds is 300-350 DEG C.
6. a kind of preparation method rich in mesopore asphalt-base globular active carbon as claimed in claim 1, it is characterised in that described
Organic solvent includes the one or more in methanol, ethanol, ethylene glycol and acetone, and the solvent added is with containing mesophase pitch
The weight ratio of powder is 0.5-3.
7. a kind of preparation method rich in mesopore asphalt-base globular active carbon as claimed in claim 6, it is characterised in that described
Organic solvent and the weight ratio containing mesophase pitch powder are 1.5-2.
8. a kind of preparation method rich in mesopore asphalt-base globular active carbon as claimed in claim 1, it is characterised in that described
The addition of surface active agent polyvinyl alcohol and water is polyvinyl alcohol：Water：Weight ratio containing mesophase pitch powder is 2.5-50：
500-1000：10.
9. a kind of preparation method rich in mesopore asphalt-base globular active carbon as claimed in claim 1, it is characterised in that described
Polyvinyl alcohol：Water：Weight ratio containing mesophase pitch powder is 10-30：600-800：10.
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| CN201711043551.6A CN107720747B (en) | 2017-10-31 | 2017-10-31 | Preparation method of mesoporous-asphalt-based spherical activated carbon |
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| CN201711043551.6A CN107720747B (en) | 2017-10-31 | 2017-10-31 | Preparation method of mesoporous-asphalt-based spherical activated carbon |
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| CN110743524A (en) * | 2019-10-15 | 2020-02-04 | 华东理工大学 | Surface high-alkalinity spherical active carbon ozone catalyst and application thereof |
| CN111547721A (en) * | 2020-05-09 | 2020-08-18 | 中国铝业股份有限公司 | Preparation method of mesoporous activated carbon for supercapacitor |
| CN113582159A (en) * | 2021-09-29 | 2021-11-02 | 天津师范大学 | High-capacitance porous carbon material and preparation method thereof |
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| CN113582159A (en) * | 2021-09-29 | 2021-11-02 | 天津师范大学 | High-capacitance porous carbon material and preparation method thereof |
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