CN104909364B - With CO high2The preparation method of the high intensity grade polyacrylonitrile-radical spheric active carbon of adsorbance - Google Patents
With CO high2The preparation method of the high intensity grade polyacrylonitrile-radical spheric active carbon of adsorbance Download PDFInfo
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Abstract
One kind has CO high2The preparation method of the high intensity grade polyacrylonitrile-radical spheric active carbon of adsorbance is to mix acrylonitrile, aqueous gelatin solution or polyvinyl alcohol water solution, acrylamide and acrylonitrile to obtain emulsion phase；By styrene derivative, divinylbenzene and azodiisobutyronitrile mixing and stirring obtain oil phase, and oil phase is added dropwise in emulsion phase, and completion of dropping solidify afterwards obtain resin balls, with resin balls of the air after 310 350 DEG C and the 5h of constant temperature 1 must be crosslinked；Crosslinked resin ball carbonization-activation is obtained into millimetre-sized activated carbon ball.The present invention has that intensity is higher, CO2The stronger advantage of adsorption capacity.
Description
Technical field
There is CO high the invention belongs to one kind2The preparation of the high intensity grade polyacrylonitrile-radical spheric active carbon of adsorbance
Method.
Background technology
Greenhouse gases CO2Removing be current global range scientist research focus, in particular for capture flue gas
The CO of middle effusion2, each show his special prowess for scientists from all over the world, and various methods have had been developed, but topmost method is two classes：One is liquid
Ammonia catching method, another kind is solid adsorption processes.The latter is considered as the method for most promotion prospect.From flue gas
Gas volume it is huge, then be suitable for fume treatment is recirculating fluidized bed, but to adsorbent therein requirement it is very high, especially
It is higher to sphere diameter size and wear requirements.Spheric active carbon is regular spherical, its abrasion each other due to its appearance
Significantly lower than other shapes of activated carbon, therefore spheric active carbon is more suitable for the CO in recirculating fluidized bed2Capturing agent.
Many research shows that activated carbon surface and the body phase activated carbon rich in nitrogen are to acid CO2Capture is extremely
Favorably, it is how more to be fixed to nitrogen on activated carbon as research key by this.Wherein using rich in before nitrogen
It is preferably selection that body prepares activated carbon.Polyacrylonitrile is due to containing more nitrogen, and its carbonization yield is also significantly high
In other itrogenous organic substances, therefore it turns into most suitable precursor.
The research for preparing spheric active carbon as presoma with polyacrylonitrile at present is less, and the polyacrylonitrile for obtaining is mainly
Nanometer and micron level, are not suitable for being used in recirculating fluidized bed, and it remains as resin balls, is not yet changed into adsorbable
CO2Activated carbon.
Inventor herein has applied for the patent of multinomial millimeter activated carbon beads, such as Patent No. 201010564568.8
" a kind of preparation method of millimeter activated carbon beads ", its preparation method is as follows：By the polyacrylonitrile of 1-5 mass parts in 10-50
Fully dissolved in the technical grade dimethyl sulfoxide (DMSO) (DMSO) of mass parts, be subsequently adding the rare-earth salts of 0.01-0.5 mass parts, fully
Stirring mixing.Solution is gradually transferred in fluid extruding device, in solution is instilled coagulating bath at identical conditions, doping is obtained dilute
The spherical polyacrylonitrile resin of soil.The millimeter of diameter about 1-3mm is further obtained by low-temperature oxidation, charing, steam activation
Level mesoporous carbon bead.But the sphericity of patent gained bead is general, it is this on the basis of this patent and has carried out continuation and change
Enter, i.e. patent 201210123527.4 " there is the preparation method of the grade polyacrylonitrile bead of good sphericity ", by changing
Become polyacrylonitrile coagulator and prepare the grade polyacrylonitrile bead with good sphericity, although not carrying out follow-up preparation
The method of spheric active carbon, but presoma heredity will make follow-up activated charcoal pellets sphericity aspect will not occur significantly
Change.For for CO2Capture, a kind of " CO of Patent No. 201410560658.8 has been invented again2Absorption grade
The preparation method of polyacrylonitrile-radical spheric active carbon " patent, as a result of the N containing primary amino radical, N- methylene bisacrylamide acyls
Amine is polymerized with acrylonitrile, and all follow-up operation temperatures are carried out at a lower temperature, therefore the nitrogen of final products contains
Amount is higher, it is ensured that product is to CO2High absorption property, obtain CO2Quantity of the catch is up to 16.5wt%, crushing strength up to 5.5N's
Good result, but still have the improvement rising space.
The content of the invention
It is an object of the invention to provide a kind of intensity is higher, CO2The stronger grade polyacrylonitrile-radical of adsorption capacity is spherical
The preparation method of activated carbon.
The method of the present invention comprises the following steps：
(1) configuration of emulsion phase and oil phase：On the basis of acrylonitrile quality, 5-15 times of acrylonitrile quality of water is weighed,
The aqueous gelatin solution of 0.4-0.8wt% concentration or the polyvinyl alcohol water solution of 1-5wt% concentration are prepared, in gelatin water or polyethylene
The acrylamide and acrylonitrile of the 2-8% of acrylonitrile quality are added in alcohol solution, stirring obtains emulsion phase；Weigh acrylonitrile
The styrene derivative of the 10-35% of quality, the divinylbenzene and total monomer quality 0.5- of the 3-15% of acrylonitrile quality
2% azodiisobutyronitrile, mixes, is uniformly mixing to obtain oil phase, and wherein total monomer is that acrylonitrile, acrylamide, styrene spread out
Biological, divinylbenzene sum；
(2) preparation of resin balls：The mass ratio of emulsion phase and oil phase is 13-120, by emulsion stirring in 300-500rmp
Mixing after be raised to 60-75 DEG C under speed, oil phase being added dropwise with the speed of 5-10ml/h, constant temperature stirring 2- at this temperature after completion of dropping
4h, then it is increased to 85-100 DEG C, isothermal curing 1-3h obtains final product resin balls；
(3) crosslinking of resin balls：According to patent 201210123598.4, " one kind slows down grade polyacrylonitrile bead and aoxidizes
The method of the method for rupture " is aoxidized, i.e., be raised to 310-350 DEG C and constant temperature with the heating rate of 1-10 DEG C/h with excess air
1-5h, that is, be obtained the resin balls after crosslinking；
(4) preparation of spheric active carbon：Crosslinked resin ball is raised to 500-700 DEG C with 2-5 DEG C/min in an inert atmosphere
Charing 0.5-2h, obtains carbonizing ball, is dissolved in the deionized water of its 2-10 times of quality according to the KOH of 1-3 parts of quality preparing afterwards
Into the aqueous solution, the charing ball of 1 part of quality is added to be sufficiently impregnated, the mixture is in N afterwards2It is raised to 3-8 DEG C/min in atmosphere
500-700 DEG C of activation 1-3h, then cooling to be drying to obtain after wash neutrality with a large amount of deionized waters after room temperature it is millimetre-sized
Activated carbon ball.
Styrene derivative is as described above：P-nitrophenyl ethene, p-aminophenyl ethene, p-chloromethyl styrene or right
Sulfonic benzo ethene.
Advantages of the present invention：The different several macromolecules of reactivity ratio can be realized molecule by 1 method as a result of being added dropwise
Than more uniform distribution on chain, so especially nitrogen content aspect has and is obviously improved the performance of gained sample, it is ensured that competing
The relatively low acrylonitrile of poly- rate and acrylamide can be more grafted in the chain of styrene and divinylbenzene；
2, by graft phenylethene and divinylbenzene on polyacrylonitrile strand, can be obviously improved the intensity of sample, this hair
The maximum intensity of bright middle sample reaches 12.5N；
3 is different from the patent for preparing grade polyacrylonitrile bead before due to pelletizing method, in gained sample hardly
Hole containing tunnel-like, the heap density of so gained sample is also obviously improved, while raising and gas to intensity
Adsorbance is highly advantageous；
Employing the macromolecule containing nitrogen, element sulphur in 4 present invention as far as possible carries out copolyreaction, in gained sample
Nitrogen and sulphur are will be enriched in, will so be greatly promoted to CO2Quantity of the catch, up to 4.2mmol/g；
Main based on polyacrylonitrile on 5 copolymerized macromolecule chains of the invention, the quantity of styrene and divinylbenzene is relative
Less, the crosslinking so to the strand of acrylonitrile-acrylamide-styrene-divinylbenzene can use simple air oxygen
The method of change, without using concentrated acid sulfonation method, the latter will unavoidably produce substantial amounts of spent acid, while sulfonation expense knot
Still needed after beam gradient elution to be carried out, cause being substantially improved for workload and dramatically increasing for cost；
6 present invention have easy to operate, it is easy to the advantages of controlling.
Specific embodiment
The crushing strength of embodiment is determined using patent 200820105920.X " simple grain spheric granules crushing strength measure
Instrument " method：The spheric active carbon 26 of a diameter of 1.5mm is chosen, the single pellet crush that spheric active carbon is measured on intensity meter is strong
Degree, casts out maximum, each three of minimum value, calculates the average value of 20.It is repeated 3 times, then averages strong as the crushing of simple grain
Degree.
CO2Adsorbance is tested：In CO2When content is 100%, 30 DEG C of test temperature, gas pressure 1atm, using gravimetric method
Test.
The standard sub-sieve that gained activated carbon ball crosses different size between 12-60 mesh is sieved, and calculates screening gained living
Property charcoal ball accounts for the mass ratio of gross activity charcoal ball.
Embodiment 1
0.3g gelatin is dissolved in 75g hot water, 15g acrylonitrile, 0.3g acrylamides is added, emulsion is uniformly mixing to obtain
Phase；1.8g p-nitrophenyls ethene, 2.25g divinylbenzenes and 0.387g azodiisobutyronitriles are mixed, oil is uniformly mixing to obtain
Phase；After emulsion is raised into 75 DEG C under 400rmp mixing speeds, start be added dropwise oil phase, with 5.0ml/h speed completion of dropping after,
Constant temperature stirring 2h at this temperature after completion of dropping, then it is increased to 85 DEG C, isothermal curing 3h obtains final product resin balls；Use excess air
310 DEG C and constant temperature 5h are raised to the heating rate of 1 DEG C/h, that is, the resin balls after crosslinking are obtained；By crosslinked resin ball in indifferent gas
600 DEG C of charing 1h are raised to 2 DEG C/min in atmosphere, obtain carbonizing ball, be dissolved in its 3 times of quality according to the KOH of 1 part of quality afterwards
The aqueous solution is configured in deionized water, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2With 8 in atmosphere
DEG C/min is raised to 700 DEG C of activation 1h, then cooling to and be drying to obtain millimeter after wash neutrality with a large amount of deionized waters after room temperature
The activated carbon ball of level.
The activated carbon ball ratio of gained 16-20 mesh is 92.7%, and crushing strength is 6.5N；The product is to CO2Quantity of the catch
It is 3.2mmol/g.
Embodiment 2
13.5g polyvinyl alcohol is dissolved in 270g water, 18g acrylonitrile, 1.44g acrylamides is added, is uniformly mixing to obtain
Emulsion phase；6.3g p-sulfonic acid bases styrene, 2.7g divinylbenzenes and 0.142g azodiisobutyronitriles are mixed, is stirred
To oil phase；After emulsion is raised into 60 DEG C under 300rmp mixing speeds, start that oil phase is added dropwise, dripped with 10.0ml/h speed
Bi Hou, constant temperature stirring 4h at this temperature after completion of dropping, then it is increased to 100 DEG C, isothermal curing 1h obtains final product resin balls；It is used
Amount air is raised to 350 DEG C and constant temperature 1h with the heating rate of 10 DEG C/h, that is, the resin balls after crosslinking are obtained；Crosslinked resin ball is existed
In inert atmosphere with 2 DEG C/min be raised to 500 DEG C charing 2.0h, obtain carbonize ball, afterwards according to the KOH of 3 parts of quality be dissolved in its 10
The aqueous solution is configured in the deionized water of times quality, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2Gas
500 DEG C of activation 3h are raised to 3 DEG C/min in atmosphere, drying is then cooled to after wash neutrality with a large amount of deionized waters after room temperature i.e.
Obtain millimetre-sized activated carbon ball.
The activated carbon ball ratio of gained 20-30 mesh is 96.3%, and crushing strength is 7.2N；The product is to CO2Quantity of the catch
It is 3.8mmol/g.
Embodiment 3
1.2g polyvinyl alcohol is dissolved in 120g water, 20g acrylonitrile, 0.4g acrylamides is added, breast is uniformly mixing to obtain
Liquid phase；7.0g p-aminophenyls ethene, 0.6g divinylbenzenes and 0.56g azodiisobutyronitriles are mixed, oil is uniformly mixing to obtain
Phase；After emulsion is raised into 75 DEG C under 300rmp mixing speeds, start that oil phase is added dropwise, after 5ml/h speed completion of dropping, drop
Constant temperature stirring 2h at this temperature is added after finishing, then is increased to 100 DEG C, isothermal curing 1h obtains final product resin balls；With excess air with
The heating rate of 10 DEG C/h is raised to 310 DEG C and constant temperature 5h, that is, the resin balls after crosslinking are obtained；By crosslinked resin ball in inert atmosphere
In with 3 DEG C/min be raised to 700 DEG C charing 0.5h, obtain carbonize ball, be dissolved in its 3 times of quality according to the KOH of 1.5 parts of quality afterwards
The aqueous solution is configured in deionized water, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2With 3 in atmosphere
DEG C/min is raised to 600 DEG C of activation 1h, then cooling to and be drying to obtain millimeter after wash neutrality with a large amount of deionized waters after room temperature
The activated carbon ball of level.
The activated carbon ball ratio of gained 14-16 mesh is 94.6%, and crushing strength is 12.5N；Quantity of the catch of the product to CO2
It is 4.2mmol/g.
Embodiment 4
8.25g polyvinyl alcohol is dissolved in 165g water, 20g acrylonitrile, 0.72g acrylamides is added, is uniformly mixing to obtain
Emulsion phase；2.0g p-sulfonic acid bases styrene, 3.0g divinylbenzenes and 0.386g azodiisobutyronitriles are mixed, is stirred
To oil phase；After emulsion is raised into 75 DEG C under 500rmp mixing speeds, start that oil phase is added dropwise, with 10ml/h speed completion of dropping
Afterwards, constant temperature stirring 2h at this temperature after completion of dropping, then it is increased to 90 DEG C, isothermal curing 3h obtains final product resin balls；Use excessive sky
Gas is raised to 330 DEG C and constant temperature 3h with the heating rate of 10 DEG C/h, that is, the resin balls after crosslinking are obtained；By crosslinked resin ball in inertia
500 DEG C of charing 2h are raised to 5 DEG C/min in atmosphere, obtain carbonizing ball, be dissolved in its 2 times of quality according to the KOH of 3 parts of quality afterwards
The aqueous solution is configured in deionized water, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2With 3 in atmosphere
DEG C/min is raised to 500 DEG C of activation 2h, then cooling to and be drying to obtain millimeter after wash neutrality with a large amount of deionized waters after room temperature
The activated carbon ball of level.
The activated carbon ball ratio of gained 16-20 mesh is 93.9%, and crushing strength is 11.4N；The product is to CO2Quantity of the catch
It is 3.9mmol/g.
Embodiment 5
0.72g gelatin is dissolved in 90g water, 18g acrylonitrile, 0.36g acrylamides is added, emulsion is uniformly mixing to obtain
Phase；6.3g p-chloromethyl styrenes, 0.54g divinylbenzenes and 0.126g azodiisobutyronitriles are mixed, is uniformly mixing to obtain
Oil phase；After emulsion is raised into 75 DEG C under 500rmp mixing speeds, start be added dropwise oil phase, with 9ml/h speed completion of dropping after,
Constant temperature stirring 2h at this temperature after completion of dropping, then it is increased to 85 DEG C, isothermal curing 3h obtains final product resin balls；Use excess air
350 DEG C and constant temperature 1h are raised to the heating rate of 9 DEG C/h, that is, the resin balls after crosslinking are obtained；By crosslinked resin ball in indifferent gas
700 DEG C of charing 0.5h are raised to 5 DEG C/min in atmosphere, obtain carbonizing ball, be dissolved in its 5 times of quality according to the KOH of 3 parts of quality afterwards
The aqueous solution is configured in deionized water, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2With 8 in atmosphere
DEG C/min is raised to 700 DEG C of activation 1h, then cooling to and be drying to obtain millimeter after wash neutrality with a large amount of deionized waters after room temperature
The activated carbon ball of level.
The activated carbon ball ratio of gained 25-35 mesh is 95.1%, and crushing strength is 5.5N；The product is to CO2Quantity of the catch
It is 3.3mmol/g.
Embodiment 6
14.40g polyvinyl alcohol is dissolved in 288g water, 36g acrylonitrile, 2.83g acrylamides is added, is uniformly mixing to obtain
Emulsion phase；11.16g p-sulfonic acid bases styrene, 4.68g divinylbenzenes and 0.825g azodiisobutyronitriles are mixed, stirring is equal
It is even to obtain oil phase；After emulsion is raised into 70 DEG C under 350rmp mixing speeds, start that oil phase is added dropwise, be added dropwise with 8ml/h speed
After finishing, constant temperature stirring 2h at this temperature after completion of dropping, then it is increased to 85 DEG C, isothermal curing 3h obtains final product resin balls；With
Excess air is raised to 320 DEG C and constant temperature 4h with the heating rate of 10 DEG C/h, that is, the resin balls after crosslinking are obtained；By crosslinked resin ball
In an inert atmosphere with 3 DEG C/min be raised to 500 DEG C charing 2h, obtain carbonize ball, afterwards according to the KOH of 2.5 parts of quality be dissolved in its 4
The aqueous solution is configured in the deionized water of times quality, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2Gas
600 DEG C of activation 1h are raised to 5 DEG C/min in atmosphere, drying is then cooled to after wash neutrality with a large amount of deionized waters after room temperature i.e.
Obtain millimetre-sized activated carbon ball.
The activated carbon ball ratio of gained 18-25 mesh is 95.4%, and crushing strength is 9.2N；The product is to CO2Quantity of the catch
It is 4.1mmol/g.
Embodiment 7
1.92g gelatin is dissolved in 270g water, 36g acrylonitrile, 0.864g acrylamides is added, emulsion is uniformly mixing to obtain
Phase；7.92 p-aminophenyl ethene, 5.04g divinylbenzenes and 0.648g azodiisobutyronitriles are mixed, oil is uniformly mixing to obtain
Phase；After emulsion is raised into 60 DEG C under 500rmp mixing speeds, start be added dropwise oil phase, with 5.0ml/h speed completion of dropping after,
Constant temperature stirring 3h at this temperature after completion of dropping, then it is increased to 100 DEG C, isothermal curing 2h obtains final product resin balls；Use excess air
310 DEG C and constant temperature 5h are raised to the heating rate of 1 DEG C/h, that is, the resin balls after crosslinking are obtained；By crosslinked resin ball in indifferent gas
600 DEG C of charing 1h are raised to 5 DEG C/min in atmosphere, obtain carbonizing ball, be dissolved in going for its 2 times of quality according to the KOH of 1 part of quality afterwards
The aqueous solution is configured in ionized water, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2In atmosphere with 3 DEG C/
Min is raised to 700 DEG C of activation 1h, then cooling to be drying to obtain after wash neutrality with a large amount of deionized waters after room temperature it is millimetre-sized
Activated carbon ball.
The activated carbon ball ratio of gained 30-50 mesh is 96.2%, and crushing strength is 5.1N；The product is to CO2Quantity of the catch
It is 3.75mmol/g.
Embodiment 8
20.0g polyvinyl alcohol is dissolved in 400g water, 40g acrylonitrile, 2.8g acrylamides is added, breast is uniformly mixing to obtain
Liquid phase；13.38g p-nitrophenyls ethene, 5.62g divinylbenzenes and 0.685g azodiisobutyronitriles are mixed, is stirred
To oil phase；After emulsion is raised into 75 DEG C under 400rmp mixing speeds, start that oil phase is added dropwise, with 7ml/h speed completion of dropping
Afterwards, constant temperature stirring 4h at this temperature after completion of dropping, then it is increased to 85 DEG C, isothermal curing 3h obtains final product resin balls；Use excessive sky
Gas is raised to 340 DEG C and constant temperature 2h with the heating rate of 10 DEG C/h, that is, the resin balls after crosslinking are obtained；By crosslinked resin ball in inertia
550 DEG C of charing 1.5h are raised to 5 DEG C/min in atmosphere, obtain carbonizing ball, be dissolved in its 3 times of quality according to the KOH of 1 part of quality afterwards
Deionized water in be configured to the aqueous solution, add the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2In atmosphere with
5 DEG C/min is raised to 700 DEG C of activation 1h, then cooling to and being drying to obtain after wash neutrality with a large amount of deionized waters after room temperature in the least
The activated carbon ball of meter level.
The activated carbon ball ratio of gained 14-20 mesh is 94.1%, and crushing strength is 12.1N；The product is to CO2Quantity of the catch
It is 3.3mmol/g.
Embodiment 9
3.69g gelatin is dissolved in 560g water, 64g acrylonitrile, 1.42g acrylamides is added, emulsion is uniformly mixing to obtain
Phase；18.56g p-aminophenyls ethene, 9.36g divinylbenzenes and 0.816g azodiisobutyronitriles are mixed, is uniformly mixing to obtain
Oil phase；After emulsion is raised into 65 DEG C under 500rmp mixing speeds, start that oil phase is added dropwise, with 10ml/h speed completion of dropping
Afterwards, constant temperature stirring 4h at this temperature after completion of dropping, then it is increased to 90 DEG C, isothermal curing 2.5h obtains final product resin balls；With excess
Air is raised to 330 DEG C and constant temperature 3h with the heating rate of 6 DEG C/h, that is, the resin balls after crosslinking are obtained；By crosslinked resin ball lazy
Property atmosphere in 3 DEG C/min be raised to 600 DEG C charing 1h, obtain carbonize ball, be dissolved in its 10 times of matter according to the KOH of 3 parts of quality afterwards
The aqueous solution is configured in the deionized water of amount, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2In atmosphere
600 DEG C of activation 1.5h are raised to 3 DEG C/min, then being cooled to and being drying to obtain after wash neutrality with a large amount of deionized waters after room temperature
Millimetre-sized activated carbon ball.
The activated carbon ball ratio of gained 18-20 mesh is 93.5%, and crushing strength is 10.5N；The product is to CO2Quantity of the catch
It is 3.7mmol/g.
Embodiment 10
12.25g polyvinyl alcohol is dissolved in 500g water, 56g acrylonitrile, 1.25g acrylamides is added, is uniformly mixing to obtain
Emulsion phase；19.18g p-sulfonic acid bases styrene, 6.55g divinylbenzenes and 0.78g azodiisobutyronitriles are mixed, is stirred
Obtain oil phase；After emulsion is raised into 70 DEG C under 400rmp mixing speeds, start that oil phase is added dropwise, dripped with 10ml/h speed
Bi Hou, constant temperature stirring 2h at this temperature after completion of dropping, then it is increased to 90 DEG C, isothermal curing 2.5h obtains final product resin balls；It is used
Amount air is raised to 350 DEG C and constant temperature 1h with the heating rate of 9 DEG C/h, that is, the resin balls after crosslinking are obtained；Crosslinked resin ball is existed
600 DEG C of charing 1h are raised to 2 DEG C/min in inert atmosphere, obtain carbonizing ball, be dissolved in its 5 times of matter according to the KOH of 2 parts of quality afterwards
The aqueous solution is configured in the deionized water of amount, adds the charing ball of 1 part of quality to be sufficiently impregnated, the mixture is in N afterwards2In atmosphere
700 DEG C of activation 1h are raised to 8 DEG C/min, then being cooled to and being drying to obtain after wash neutrality with a large amount of deionized waters after room temperature in the least
The activated carbon ball of meter level.
The activated carbon ball ratio of gained 14-18 mesh is 91.9%, and crushing strength is 11.7N；The product is to CO2Quantity of the catch
It is 3.8mmol/g.
Claims (2)
1. it is a kind of that there is CO high2The preparation method of the high intensity grade polyacrylonitrile-radical spheric active carbon of adsorbance, its feature exists
In comprising the following steps：
(1) configuration of emulsion phase and oil phase：On the basis of acrylonitrile quality, 5-15 times of acrylonitrile quality of water is weighed, prepared
The aqueous gelatin solution of 0.4-0.8wt% concentration or the polyvinyl alcohol water solution of 1-5wt% concentration, in aqueous gelatin solution or polyvinyl alcohol
The acrylamide and acrylonitrile of the 2-8% of acrylonitrile quality are added in the aqueous solution, stirring obtains emulsion phase；Weigh acrylonitrile matter
The styrene derivative of the 10-35% of amount, the divinylbenzene of the 3-15% of acrylonitrile quality and total monomer quality 0.5-2%'s
Azodiisobutyronitrile, mixes, is uniformly mixing to obtain oil phase, wherein total monomer be acrylonitrile, acrylamide, styrene derivative,
Divinylbenzene sum；
(2) preparation of resin balls：The mass ratio of emulsion phase and oil phase is 13-120, and emulsion is fast in the stirring of 300-500rmp
After being raised to 60-75 DEG C under degree, oil phase is added dropwise with the speed of 5-10ml/h, constant temperature stirs 2-4h at this temperature after completion of dropping,
85-100 DEG C is increased to again, and isothermal curing 1-3h obtains final product resin balls；
(3) crosslinking of resin balls：310-350 DEG C and constant temperature 1-5h is raised to the heating rate of 1-10 DEG C/h with excess air, i.e.,
The resin balls after crosslinking are obtained；
(4) preparation of spheric active carbon：Crosslinked resin ball is raised to 500-700 DEG C of charing with 2-5 DEG C/min in an inert atmosphere
0.5-2h, obtains carbonizing ball, is dissolved in the deionized water of its 2-10 times of quality according to the KOH of 1-3 parts of quality is configured to water afterwards
Solution, adds the charing ball of 1 part of quality to be sufficiently impregnated, and the mixture is in N afterwards2500-700 is raised to 3-8 DEG C/min in atmosphere
DEG C activation 1-3h, then cooling to and be drying to obtain millimetre-sized activated carbon after wash neutrality with a large amount of deionized waters after room temperature
Ball.
2. as claimed in claim 1 a kind of with CO high2The high intensity grade polyacrylonitrile-radical spheric active carbon of adsorbance
Preparation method, it is characterised in that described styrene derivative be p-nitrophenyl ethene, p-aminophenyl ethene, to chloromethylbenzene second
Alkene or p-sulfonic acid base styrene.
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| JPS6481890A (en) * | 1987-09-24 | 1989-03-28 | Nippon Carbon Co Ltd | Porous carbonaceous spherule and production thereof |
| CN1938223A (en) * | 2004-03-30 | 2007-03-28 | 株式会社吴羽 | Process for producing spherical carbon material |
| CN101983918A (en) * | 2010-11-25 | 2011-03-09 | 中国科学院山西煤炭化学研究所 | Preparation method of millimeter activated carbon beads |
| CN102666376A (en) * | 2009-12-24 | 2012-09-12 | 东丽株式会社 | Carbon microparticle and process for production thereof |
| CN104310395A (en) * | 2014-10-21 | 2015-01-28 | 中国科学院山西煤炭化学研究所 | Preparation method of millimeter-sized polyacrylonitrile-base spherical active carbon for adsorbing carbon dioxide (CO2) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2001083368A1 (en) * | 2000-04-28 | 2001-11-08 | Bluecher Hasso Von | Method for producing spherical activated carbon |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6481890A (en) * | 1987-09-24 | 1989-03-28 | Nippon Carbon Co Ltd | Porous carbonaceous spherule and production thereof |
| CN1938223A (en) * | 2004-03-30 | 2007-03-28 | 株式会社吴羽 | Process for producing spherical carbon material |
| CN102666376A (en) * | 2009-12-24 | 2012-09-12 | 东丽株式会社 | Carbon microparticle and process for production thereof |
| CN101983918A (en) * | 2010-11-25 | 2011-03-09 | 中国科学院山西煤炭化学研究所 | Preparation method of millimeter activated carbon beads |
| CN104310395A (en) * | 2014-10-21 | 2015-01-28 | 中国科学院山西煤炭化学研究所 | Preparation method of millimeter-sized polyacrylonitrile-base spherical active carbon for adsorbing carbon dioxide (CO2) |
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