CN104909364A - Preparation method of high-strength millimeter-scale polyacrylonitrile-based spherical active carbon with high CO2 adsorbing capacity - Google Patents
Preparation method of high-strength millimeter-scale polyacrylonitrile-based spherical active carbon with high CO2 adsorbing capacity Download PDFInfo
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- CN104909364A CN104909364A CN201510311997.7A CN201510311997A CN104909364A CN 104909364 A CN104909364 A CN 104909364A CN 201510311997 A CN201510311997 A CN 201510311997A CN 104909364 A CN104909364 A CN 104909364A
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Abstract
The invention relates to a preparation method of high-strength millimeter-scale polyacrylonitrile-based spherical active carbon with high CO2 adsorbing capacity. The preparation method comprises the steps: mixing and stirring acrylonitrile, a gelatin aqueous solution or polyvinyl alcohol aqueous solution, acrylamide and acrylonitrile to obtain an emulsion phase; uniformly mixing and stirring a styrene derivative, divinyl benzene and azodiisobutyronitrile to obtain an oil phase, dropwise adding the oil phase into the emulsion phase, then curing to obtain resin spheres, crosslinking in the air at the temperature of 310 to 350 DEG C, and maintaining the temperature for 1 to 5 hours, thus obtaining the crosslinked resin spheres; and carbonizing and activating the crosslinked resin spheres to obtain the nano-scale active carbon spheres. The preparation method has advantages of higher strength and higher CO2 adsorbing capacity.
Description
Technical field
The invention belongs to one and there is high CO
2the preparation method of the high strength grade polyacrylonitrile-radical spheric active carbon of adsorptive capacity.
Background technology
Greenhouse gases CO
2remove be current global range scientist research focus, especially for catching the CO overflowed in stack gas
2, each show his special prowess for various countries scientist, developed multiple method, but topmost method is two classes: one is liquefied ammonia catching method, and another kind is solid adsorption processes.The latter is considered to the method most with promotion prospect.The gas volume deriving from stack gas is huge, be then suitable for fume treatment for circulating fluidized bed, but require very high to sorbent material wherein, especially to sphere diameter size and wear requirements higher.Spheric active carbon due to its appearance be regular spherical, its wearing and tearing are each other starkly lower than the gac of other shape, and therefore spheric active carbon is more suitable for as the CO in circulating fluidized bed
2trapping agent.
Many research shows, the gac of activated carbon surface and the mutually equal rich Nitrogen element of body is to the CO of acidity
2catch very favourable, how nitrogen element is more fixed to that gac to become research crucial for this reason.Wherein adopting the precursor of rich Nitrogen element to prepare gac is good selection.Polyacrylonitrile is due to containing more nitrogen element, and its carbonization yield is also significantly higher than other itrogenous organic substance, therefore it becomes most suitable precursor.
The research with polyacrylonitrile being at present precursor power spheric active carbon is less, and the polyacrylonitrile obtained mainly nanometer and micron level, be not suitable for using in circulating fluidized bed, and it is still resin balls, not yet changes adsorbable CO into
2gac.
Inventor herein has applied for the patent of multinomial millimeter activated carbon beads, if the patent No. is 201010564568.8 " a kind of preparation methods of millimeter activated carbon beads ", its preparation method is as follows: fully dissolved in the technical grade dimethyl sulfoxide (DMSO) (DMSO) of 10-50 mass parts by the polyacrylonitrile of 1-5 mass parts, then add the rare-earth salts of 0.01-0.5 mass parts, be fully uniformly mixed.Solution is transferred in fluid extruding device gradually, solution is instilled in precipitation bath at identical conditions, obtain rare earth doped spherical polyacrylonitrile resin.The grade mesoporous carbon bead that diameter is about 1-3mm is obtained further by low-temperature oxidation, charing, steam activation.But the sphericity of this patent gained bead is general, on this patent basis, carried out persistence improvement again for this reason, i.e. patent 201210123527.4 " there is the preparation method of the grade polyacrylonitrile bead of good sphericity ", the grade polyacrylonitrile bead with good sphericity is prepared by changing polyacrylonitrile peptizer, although do not carry out the follow-up method preparing spheric active carbon, can not there is significant change by making the sphericity aspect of follow-up activated charcoal pellets in the heredity of presoma.For for CO
2catch, invented again " a kind of CO that the patent No. is 201410560658.8
2the absorption preparation method of grade polyacrylonitrile-radical spheric active carbon " patent; owing to have employed the N containing primary amino; N-methylene-bisacrylamide is polymerized with vinyl cyanide; and all follow-up service temperatures are carried out all at a lower temperature; therefore the nitrogen content of the finished product is higher, ensure that product is to CO
2high absorption property, obtain CO
2the good result that quantity of the catch reaches 16.5wt%, crushing strength reaches 5.5N, but still have the improvement rising space.
Summary of the invention
The object of this invention is to provide that a kind of intensity is higher, CO
2the preparation method of the grade polyacrylonitrile-radical spheric active carbon that adsorptive power is stronger.
Method of the present invention comprises the steps:
(1) configuration of emulsion phase and oil phase: with vinyl cyanide quality for benchmark, take the 5-15 water doubly of vinyl cyanide quality, the aqueous gelatin solution of preparation 0.4-0.8wt% concentration or the polyvinyl alcohol water solution of 1-5wt% concentration, in gelatin water or polyvinyl alcohol water solution, add acrylamide and the vinyl cyanide of the 2-8% of vinyl cyanide quality, stir and obtain emulsion phase; Take the styrene derivatives of the 10-35% of vinyl cyanide quality, the Vinylstyrene of the 3-15% of vinyl cyanide quality and the Diisopropyl azodicarboxylate of total monomer quality 0.5-2%, mix, stirring obtains oil phase, wherein total monomer is vinyl cyanide, acrylamide, styrene derivatives, Vinylstyrene sum;
(2) preparation of resin balls: the mass ratio of emulsion phase and oil phase is 13-120, after emulsion is raised to 60-75 DEG C under the stirring velocity of 300-500rmp, oil phase is dripped with the speed of 5-10ml/h, after dropwising, constant temperature stirs 2-4h at this temperature, be elevated to 85-100 DEG C again, isothermal curing 1-3h, obtains resin balls;
(3) resin balls is crosslinked: be oxidized according to the method for patent 201210123598.4 " a kind of method slowing down grade polyacrylonitrile bead oxide breaks ", namely use excess air to be raised to 310-350 DEG C and constant temperature 1-5h with the temperature rise rate of 1-10 DEG C/h, namely obtain the resin balls after being cross-linked;
(4) preparation of spheric active carbon: cross-linked resin ball is raised to 500-700 DEG C of charing 0.5-2h with 2-5 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved in the deionized water of its 2-10 times quality according to the KOH of 1-3 part quality afterwards and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2500-700 DEG C of activation 1-3h is raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 3-8 DEG C/min in atmosphere.
Styrene derivatives as above is: p-nitrophenyl ethene, p-aminophenyl ethene, p-chloromethyl styrene or p-sulfonic acid base vinylbenzene.
Advantage of the present invention: 1 owing to have employed the method for dropping, several polymers different for reactivity ratio can be realized molecular chain distributes more uniformly, the performance of such gained sample especially has significant lifting in nitrogen content aspect, can ensure that the vinyl cyanide that reactivity ratio is lower and acrylamide can more be grafted in the chain of vinylbenzene and divinylbenzene;
2 by graft phenylethene and divinylbenzene on polyacrylonitrile molecular chain, and significantly can promote the intensity of sample, in the present invention, the maximum intensity of sample reaches 12.5N;
3 due to pelletizing method different from the patent preparing grade polyacrylonitrile bead before, hole hardly containing tunnel-like in gained sample, the bulk density of such gained sample is also promoted significantly, simultaneously to the raising of intensity and the adsorptive capacity of gas all very favourable;
The polymer that have employed as far as possible in 4 the present invention containing nitrogen element, element sulphur carries out copolyreaction, will be rich in nitrogen and sulphur in gained sample, will greatly promote CO like this
2quantity of the catch, be up to 4.2mmol/g;
Main based on polyacrylonitrile on 5 copolymerized macromolecule chains of the present invention, vinylbenzene is relative with the quantity of divinylbenzene less, like this to the crosslinked method that can adopt simple atmospheric oxidation of the molecular chain of vinyl cyanide-acrylamide-styrene-divinylbenzene, and concentrated acid sulfonation method need not be adopted, the latter will unavoidably produce a large amount of spent acid, still need and will carry out gradient elution after the expense of sulfonation simultaneously terminates, cause the remarkable increase of significantly lifting and the cost of workload;
6 the present invention have easy and simple to handle, are easy to the advantages such as control.
Embodiment
The crushing strength of embodiment measures and adopts patent 200820105920.X " instrument for testing crushed strength of simple-grain spherical particles " method: choose the spheric active carbon 26 that diameter is 1.5mm, intensity meter is measured the single pellet crush strength of spheric active carbon, cast out maximum, each three of minimum value, calculate the mean value of 20.Repeat 3 times, then average as the crushing strength of simple grain.
CO
2adsorptive capacity is tested: at CO
2content is 100%, probe temperature 30 DEG C, gaseous tension 1atm time, adopt weighting method test.
The standard sub-sieve that different size between 12-60 order crossed by gained gac ball sieves, and calculates the mass ratio that screening gained gac ball accounts for gross activity charcoal ball.
Embodiment 1
0.3g gelatin is dissolved in 75g hot water, adds 15g vinyl cyanide, 0.3g acrylamide, stir and obtain emulsion phase; 1.8g p-nitrophenyl ethene, 2.25g Vinylstyrene and 0.387g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 75 DEG C under 400rmp stirring velocity, start to drip oil phase, after dropwising with 5.0ml/h speed, after dropwising, constant temperature stirs 2h at this temperature, then is elevated to 85 DEG C, and isothermal curing 3h, obtains resin balls; Be raised to 310 DEG C and constant temperature 5h by excess air with the temperature rise rate of 1 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 600 DEG C of charing 1h with 2 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 1 part of quality afterwards in the deionized water of its 3 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2700 DEG C of activation 1h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 8 DEG C/min in atmosphere.
Gained 16-20 object gac ball ratio is 92.7%, and crushing strength is 6.5N; This product is to CO
2quantity of the catch be 3.2mmol/g.
Embodiment 2
13.5g polyvinyl alcohol is dissolved in 270g water, adds 18g vinyl cyanide, 1.44g acrylamide, stir and obtain emulsion phase; 6.3g p-sulfonic acid base vinylbenzene, 2.7g Vinylstyrene and 0.142g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 60 DEG C under 300rmp stirring velocity, start to drip oil phase, after dropwising with 10.0ml/h speed, after dropwising, constant temperature stirs 4h at this temperature, then is elevated to 100 DEG C, and isothermal curing 1h, obtains resin balls; Be raised to 350 DEG C and constant temperature 1h by excess air with the temperature rise rate of 10 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 500 DEG C of charing 2.0h with 2 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 3 parts of quality afterwards in the deionized water of its 10 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2500 DEG C of activation 3h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 3 DEG C/min in atmosphere.
Gained 20-30 object gac ball ratio is 96.3%, and crushing strength is 7.2N; This product is to CO
2quantity of the catch be 3.8mmol/g.
Embodiment 3
1.2g polyvinyl alcohol is dissolved in 120g water, adds 20g vinyl cyanide, 0.4g acrylamide, stir and obtain emulsion phase; 7.0g p-aminophenyl ethene, 0.6g Vinylstyrene and 0.56g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 75 DEG C under 300rmp stirring velocity, start to drip oil phase, after dropwising with 5ml/h speed, after dropwising, constant temperature stirs 2h at this temperature, then is elevated to 100 DEG C, and isothermal curing 1h, obtains resin balls; Be raised to 310 DEG C and constant temperature 5h by excess air with the temperature rise rate of 10 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 700 DEG C of charing 0.5h with 3 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 1.5 parts of quality afterwards in the deionized water of its 3 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2600 DEG C of activation 1h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 3 DEG C/min in atmosphere.
Gained 14-16 object gac ball ratio is 94.6%, and crushing strength is 12.5N; This product is 4.2mmol/g to the quantity of the catch of CO2.
Embodiment 4
8.25g polyvinyl alcohol is dissolved in 165g water, adds 20g vinyl cyanide, 0.72g acrylamide, stir and obtain emulsion phase; 2.0g p-sulfonic acid base vinylbenzene, 3.0g Vinylstyrene and 0.386g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 75 DEG C under 500rmp stirring velocity, start to drip oil phase, after dropwising with 10ml/h speed, after dropwising, constant temperature stirs 2h at this temperature, then is elevated to 90 DEG C, and isothermal curing 3h, obtains resin balls; Be raised to 330 DEG C and constant temperature 3h by excess air with the temperature rise rate of 10 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 500 DEG C of charing 2h with 5 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 3 parts of quality afterwards in the deionized water of its 2 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2500 DEG C of activation 2h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 3 DEG C/min in atmosphere.
Gained 16-20 object gac ball ratio is 93.9%, and crushing strength is 11.4N; This product is to CO
2quantity of the catch be 3.9mmol/g.
Embodiment 5
0.72g gelatin is dissolved in 90g water, adds 18g vinyl cyanide, 0.36g acrylamide, stir and obtain emulsion phase; 6.3g p-chloromethyl styrene, 0.54g Vinylstyrene and 0.126g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 75 DEG C under 500rmp stirring velocity, start to drip oil phase, after dropwising with 9ml/h speed, after dropwising, constant temperature stirs 2h at this temperature, then is elevated to 85 DEG C, and isothermal curing 3h, obtains resin balls; Be raised to 350 DEG C and constant temperature 1h by excess air with the temperature rise rate of 9 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 700 DEG C of charing 0.5h with 5 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 3 parts of quality afterwards in the deionized water of its 5 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2700 DEG C of activation 1h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 8 DEG C/min in atmosphere.
Gained 25-35 object gac ball ratio is 95.1%, and crushing strength is 5.5N; This product is to CO
2quantity of the catch be 3.3mmol/g.
Embodiment 6
14.40g polyvinyl alcohol is dissolved in 288g water, adds 36g vinyl cyanide, 2.83g acrylamide, stir and obtain emulsion phase; 11.16g p-sulfonic acid base vinylbenzene, 4.68g Vinylstyrene and 0.825g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 70 DEG C under 350rmp stirring velocity, start to drip oil phase, after dropwising with 8ml/h speed, after dropwising, constant temperature stirs 2h at this temperature, then is elevated to 85 DEG C, and isothermal curing 3h, obtains resin balls; Be raised to 320 DEG C and constant temperature 4h by excess air with the temperature rise rate of 10 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 500 DEG C of charing 2h with 3 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 2.5 parts of quality afterwards in the deionized water of its 4 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2600 DEG C of activation 1h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 5 DEG C/min in atmosphere.
Gained 18-25 object gac ball ratio is 95.4%, and crushing strength is 9.2N; This product is to CO
2quantity of the catch be 4.1mmol/g.
Embodiment 7
1.92g gelatin is dissolved in 270g water, adds 36g vinyl cyanide, 0.864g acrylamide, stir and obtain emulsion phase; 7.92 p-aminophenyl ethene, 5.04g Vinylstyrene and 0.648g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 60 DEG C under 500rmp stirring velocity, start to drip oil phase, after dropwising with 5.0ml/h speed, after dropwising, constant temperature stirs 3h at this temperature, then is elevated to 100 DEG C, and isothermal curing 2h, obtains resin balls; Be raised to 310 DEG C and constant temperature 5h by excess air with the temperature rise rate of 1 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 600 DEG C of charing 1h with 5 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 1 part of quality afterwards in the deionized water of its 2 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2700 DEG C of activation 1h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 3 DEG C/min in atmosphere.
Gained 30-50 object gac ball ratio is 96.2%, and crushing strength is 5.1N; This product is to CO
2quantity of the catch be 3.75mmol/g.
Embodiment 8
20.0g polyvinyl alcohol is dissolved in 400g water, adds 40g vinyl cyanide, 2.8g acrylamide, stir and obtain emulsion phase; 13.38g p-nitrophenyl ethene, 5.62g Vinylstyrene and 0.685g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 75 DEG C under 400rmp stirring velocity, start to drip oil phase, after dropwising with 7ml/h speed, after dropwising, constant temperature stirs 4h at this temperature, then is elevated to 85 DEG C, and isothermal curing 3h, obtains resin balls; Be raised to 340 DEG C and constant temperature 2h by excess air with the temperature rise rate of 10 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 550 DEG C of charing 1.5h with 5 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 1 part of quality afterwards in the deionized water of its 3 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2700 DEG C of activation 1h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 5 DEG C/min in atmosphere.
Gained 14-20 object gac ball ratio is 94.1%, and crushing strength is 12.1N; This product is to CO
2quantity of the catch be 3.3mmol/g.
Embodiment 9
3.69g gelatin is dissolved in 560g water, adds 64g vinyl cyanide, 1.42g acrylamide, stir and obtain emulsion phase; 18.56g p-aminophenyl ethene, 9.36g Vinylstyrene and 0.816g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 65 DEG C under 500rmp stirring velocity, start to drip oil phase, after dropwising with 10ml/h speed, after dropwising, constant temperature stirs 4h at this temperature, then is elevated to 90 DEG C, and isothermal curing 2.5h, obtains resin balls; Be raised to 330 DEG C and constant temperature 3h by excess air with the temperature rise rate of 6 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 600 DEG C of charing 1h with 3 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 3 parts of quality afterwards in the deionized water of its 10 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2600 DEG C of activation 1.5h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 3 DEG C/min in atmosphere.
Gained 18-20 object gac ball ratio is 93.5%, and crushing strength is 10.5N; This product is to CO
2quantity of the catch be 3.7mmol/g.
Embodiment 10
12.25g polyvinyl alcohol is dissolved in 500g water, adds 56g vinyl cyanide, 1.25g acrylamide, stir and obtain emulsion phase; 19.18g p-sulfonic acid base vinylbenzene, 6.55g Vinylstyrene and 0.78g Diisopropyl azodicarboxylate are mixed, stirs and obtain oil phase; After emulsion is raised to 70 DEG C under 400rmp stirring velocity, start to drip oil phase, after dropwising with 10ml/h speed, after dropwising, constant temperature stirs 2h at this temperature, then is elevated to 90 DEG C, and isothermal curing 2.5h, obtains resin balls; Be raised to 350 DEG C and constant temperature 1h by excess air with the temperature rise rate of 9 DEG C/h, namely obtain the resin balls after being cross-linked; Cross-linked resin ball is raised to 600 DEG C of charing 1h with 2 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved according to the KOH of 2 parts of quality afterwards in the deionized water of its 5 times of quality and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2700 DEG C of activation 1h are raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 8 DEG C/min in atmosphere.
Gained 14-18 object gac ball ratio is 91.9%, and crushing strength is 11.7N; This product is to CO
2quantity of the catch be 3.8mmol/g.
Claims (2)
1. one kind has high CO
2the preparation method of the high strength grade polyacrylonitrile-radical spheric active carbon of adsorptive capacity, is characterized in that comprising the steps:
(1) configuration of emulsion phase and oil phase: with vinyl cyanide quality for benchmark, take the 5-15 water doubly of vinyl cyanide quality, the aqueous gelatin solution of preparation 0.4-0.8wt% concentration or the polyvinyl alcohol water solution of 1-5wt% concentration, in gelatin water or polyvinyl alcohol water solution, add acrylamide and the vinyl cyanide of the 2-8% of vinyl cyanide quality, stir and obtain emulsion phase; Take the styrene derivatives of the 10-35% of vinyl cyanide quality, the Vinylstyrene of the 3-15% of vinyl cyanide quality and the Diisopropyl azodicarboxylate of total monomer quality 0.5-2%, mix, stirring obtains oil phase, wherein total monomer is vinyl cyanide, acrylamide, styrene derivatives, Vinylstyrene sum;
(2) preparation of resin balls: the mass ratio of emulsion phase and oil phase is 13-120, after emulsion is raised to 60-75 DEG C under the stirring velocity of 300-500rmp, oil phase is dripped with the speed of 5-10ml/h, after dropwising, constant temperature stirs 2-4h at this temperature, be elevated to 85-100 DEG C again, isothermal curing 1-3h, obtains resin balls;
(3) resin balls is crosslinked: be raised to 310-350 DEG C and constant temperature 1-5h by excess air with the temperature rise rate of 1-10 DEG C/h, namely obtains the resin balls after being cross-linked;
(4) preparation of spheric active carbon: cross-linked resin ball is raised to 500-700 DEG C of charing 0.5-2h with 2-5 DEG C/min in an inert atmosphere, obtain carbonizing ball, be dissolved in the deionized water of its 2-10 times quality according to the KOH of 1-3 part quality afterwards and be mixed with the aqueous solution, the charing ball adding 1 part of quality fully floods, and this mixture is at N afterwards
2500-700 DEG C of activation 1-3h is raised to, with being drying to obtain millimetre-sized gac ball after a large amount of deionized water wash to neutrality after then cooling to room temperature with 3-8 DEG C/min in atmosphere.
2. one as claimed in claim 1 has high CO
2the preparation method of the high strength grade polyacrylonitrile-radical spheric active carbon of adsorptive capacity, is characterized in that described styrene derivatives is p-nitrophenyl ethene, p-aminophenyl ethene, p-chloromethyl styrene or p-sulfonic acid base vinylbenzene.
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| CN110743512A (en) * | 2019-10-30 | 2020-02-04 | 山东大学 | Preparation and regeneration method and application of carbon dioxide molecular imprinting adsorbent |
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| 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 |
|---|---|---|---|---|
| CN110743512A (en) * | 2019-10-30 | 2020-02-04 | 山东大学 | Preparation and regeneration method and application of carbon dioxide molecular imprinting adsorbent |
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