CN108658073A - A method of improving activated carbon adsorption performance - Google Patents
A method of improving activated carbon adsorption performance Download PDFInfo
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- CN108658073A CN108658073A CN201810797913.9A CN201810797913A CN108658073A CN 108658073 A CN108658073 A CN 108658073A CN 201810797913 A CN201810797913 A CN 201810797913A CN 108658073 A CN108658073 A CN 108658073A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01B32/336—Preparation characterised by gaseous activating agents
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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Abstract
The invention belongs to activated carbon preparing technical fields, and in particular to a method of improving activated carbon adsorption performance.Described method includes following steps：1) spherical polymer is subjected to sulfonation and carbonization treatment；2) product for obtaining step 1) carries out activation process；3) acidification is carried out using nitric acid to the product that step 2) obtains.The activated carbon that can make of method of the present invention has water-compatible appropriate, while modified water-compatible, while in water metallic element or the organic matter etc. that is dissolved in water there is good absorption property.
Description
Technical field
The invention belongs to activated carbon preparing technical fields, and in particular to a method of improving activated carbon adsorption performance.
Background technology
Activated carbon is a kind of common adsorbent, is black porosu solid, and pore structure is flourishing, has higher specific surface
Product, in gas, solution inorganic or organic substance and colloidal solid etc. have very strong adsorption capacity.Active Carbon in Organic
Absorption and the property of activated carbon itself, matter property, adsorption conditions have relationship, specifically include the specific surface of activated carbon
Physics and the chemical property such as product, pore-size distribution, impurity content, hydrophobicity, the content of surface functional group；The property of organic matter itself
Matter, such as polarity, hydrophobicity, molecular diameter, acidity and alkalinity；Adsorption conditions such as temperature, pH value and solvent polarity etc..Wherein influence
The most important factor of absorption is the property of activated carbon itself, especially surface functional group, it has dominated work as activated centre
Property charcoal surface chemical property, to absorption play key effect.
In order to obtain adsorption efficiency higher or the better activated carbon of adsorptive selectivity, generally require to carrying out surface
The modification of functional group, and the surface functional group of activated carbon includes mainly hydroxyl, carboxyl, ester group, phenolic hydroxyl group, aldehyde radical, ketone group, quinone
Base, quinhydrones base etc..There are mainly two types of approach for the generation of activated carbon surface functional group:When in process for preparing active carbon, not exclusively
Charing and it is remaining, this kind of reaction process is difficult to be effectively controlled；Change second is that carrying out surface chemistry to activated carbon using compound
What property was got, this kind of reaction is currently as common modified method.However existing method of modifying is usually in enhancing activated carbon table
While the polarity of face so that the affinity of activated carbon surface and water enhances.However, this method is although can be improved the water phase of activated carbon
Capacitive, but its adsorption capacity also accordingly declines.
Invention content
In order to improve the deficiencies in the prior art, the object of the present invention is to provide a kind of sides improving activated carbon adsorption performance
Method includes the following steps：
1) spherical polymer is subjected to sulfonation and carbonization treatment；
2) product for obtaining step 1) carries out activation process；
3) acidification is carried out using nitric acid to the product that step 2) obtains.
According to the present invention, in step 1), the polymer can be by mixing the polymerisation system of progress by monomer, initiator
It is standby.As example, the polymer is copolymer.Wherein, the copolymer refers to occurring to gather by the monomer of two or more
Close polymer prepared by reaction.
According to the present invention, the polymer matrix of the copolymer includes being derived from the structural unit of the first monomer and being derived from
The structural unit of second comonomer, wherein first monomer has 2~10 carbon atoms and contains at least two amino, described the
Two monomers have 4~15 carbon atoms and contain at least two carboxyls or at least one acid anhydrides.Illustratively, first monomer
Selected from aromatic diamine, aliphatic diamine；The second comonomer is selected from aromatic dicarboxylic acid anhydride, aromatic series tetra-atomic acid (two
First ester), binary aliphatic acid anhydride, aliphatic tetra-atomic acid (dibasic ester).
According to the present invention, first monomer is selected from pyromellitic acid anhydride, trimellitic anhydride, benzophenone dianhydride, biphenyl
Dianhydride, diphenyl ether dianhydride, hexafluorodianhydride (6FDA), 3,3', 4,4'- diphenyl ether tetraformic dianhydrides, 4,4'- hexafluoro isopropyl phthalic acids
Acid anhydride, 3,3', at least one of 4,4'- bibenzene tetracarboxylic dianhydrides and benzophenone tetracarboxylic dianhydride.
According to the present invention, the second comonomer is selected from ethylenediamine, propane diamine, hexamethylene diamine, p-phenylenediamine, 2,2 bis- (fluoroforms
At least one of base) benzidine.
According to the present invention, the preparation method of the polymer includes the following steps：
A) in the first polar solvent, the first monomer, second comonomer and blocking agent reaction are obtained into polyamic acid solution, institute
It is single acid anhydride containing active function groups to state end-capping reagent, and the active function groups are that may occur from by the functional group of base polymerisation；
B) make the polyamic acid solution imidization and purify, obtain polyimide prepolymer；
C) polyimide prepolymer is dissolved in the second polar solvent, radical initiator is added, is mixed
Glue cures the mixed glue solution, obtains polymer, i.e. polyimides.
According to the present invention, the reaction type for generating polyamic acid solution is known technology, and concrete operations can be, in inertia
Under gas shield, after second comonomer is dissolved in polar solvent, the first monomer is added, after reacting 1~6h, adds sealing end
Agent, wherein the half of the mole of first monomer and the mole of the end-capping reagent and single equal to described second
The mole of body, described and the quality of the gross mass and the polar solvent of monomer, first monomer and the end-capping reagent
The ratio between be 2:3, reaction 12~for 24 hours, obtain polyamic acid solution.
The inert gas uses common argon gas or nitrogen.
As the common regulation in this field, the second comonomer, the first monomer and end-capping reagent of polyamic acid solution is obtained by the reaction
In the acid anhydride containing equimolar amounts and amine functional group.
Preferably, the end-capping reagent is single acid anhydride of the active function groups of carbon-carbon double bonds or triple carbon-carbon bonds, the end-capping reagent
Molar ratio with first monomer is (2~15):250；It is highly preferred that the end-capping reagent is 4- phenylacetylene benzoic anhydrides, norborneol
Olefin(e) acid acid anhydride or phenylmaleic anhydride.The molecular weight of main chain can be effectively reduced by introducing end-capping reagent, puies forward high molecular mobility, this
Outside, there is excellent mechanical property and thermal stability by curing the polyimides generated after crosslinking.
The polyamic acid solution is carried out by imidization using method known in the art, such as can be selected
Make polyamic acid solution imidization in the presence of dehydrating agent and catalyst, specifically, the polyamic acid solution is subjected to imidization
Method include：Catalyst and dehydrating agent, the catalyst and the second comonomer are added into the polyamic acid solution
Molar ratio is (1~2.5):1, the molar ratio of the dehydrating agent and the second comonomer is (1~9):1, reaction for 24 hours, is gathered
Acid imide prepolymer solution.
Preferably, the catalyst is the mixed solution of triethylamine and pyridine, and the molar ratio of the triethylamine and pyridine is
1:8~8:1；
Preferably, the dehydrating agent is acetic anhydride.
It is known technology to carry out purification to polyimide prepolymer, and concrete operations can be that the method for the purification includes：
After the polyimide prepolymer is diluted with third polar solvent, mixed solution is obtained, the mixed solution is instilled dropwise
It is precipitated in methanol, by the washing of precipitate and filtering, and is dried, obtain polyimide prepolymer powder.
Preferably, the drying condition is using vacuum drying.
Preferably, the radical initiator is 1- hydroxycyclohexyl phenyl ketones, four mercaptoacetate of pentaerythrite, three
Polysulfide cyanic acid, 1,4- dimercaptobenzenes, 2,6- dimercaptos purine, pentaerythrite four (3-thiopropionate), azodiisobutyronitrile, mistake
One kind in Benzoyl Oxide or benzophenone, two or more.
Preferably, the cured process is：Cure 1~3h at 40~60 DEG C, cure 1~3h at 70~90 DEG C,
Cure 1~3h at 110~140 DEG C, cures 1~3h at 170~180 DEG C.
Preferably, after mixed glue solution can be granulated by comminutor, spheric granules is prepared, then cured.
Preferably, the mass ratio of the quality of the radical initiator and polyimide prepolymer is 1:(10~30).
Preferably, first polar solvent be n,N-Dimethylformamide solution, n,N-dimethylacetamide solution or
At least one of N-Methyl pyrrolidone solution；Second polar solvent is N,N-dimethylformamide solution, N, N- bis-
At least one of methyl vinyl amine aqueous solution or N-Methyl pyrrolidone solution；The third polar solvent is N, N- dimethyl methyls
At least one of amide solution, DMAC N,N' dimethyl acetamide solution or N-Methyl pyrrolidone solution.Wherein, the first polarity is molten
Agent, the second polar solvent and third polar solvent can be identical solution, or different solution.
According to the present invention, in step 1), the spherical polymer is selected from polyimides, and the polyimides is aliphatic poly
At least one of acid imide, semi-aromatic polyimides and aromatic polyimide.
According to the present invention, in step 1), the median particle diameter D of the spherical polymer50Can be 0.2-8mm, such as 0.5-
7.5mm, such as 1.5-6.0mm, such as 2.5-5.5mm, such as 4.5-4mm.The grain size of the spherical polymer can specifically be answered according to it
It is reasonably selected with environment.
According to the present invention, the polymer can also be according to known other methods prepare or it is commercially available.
According to the present invention, the polymer can be unsulfonated or the polymer of sulfonation.
According to the present invention, the not sulfonated polymer can also be prepared or commercially available according to known methods.
According to the present invention, in step 1), the sulfonation for example can be by not sulfonated spherical polymer and sulfonating agent
Contact carries out；And/or sulfonated spherical polymer and sulfonating agent are carried out.The sulfonating agent can be selected from ammonium sulfate,
Sulfuric acid (such as concentrated sulfuric acid), oleum, SO3In one or more mixtures.
According to the present invention, there is no particular limitation for the total weight ratio of not sulfonated spherical polymer and sulfonating agent, to protect
The excess of the sulfonating agent is demonstrate,proved, that is, ensures that the sulfonation of not sulfonated spherical polymer is complete；Illustratively, described not sulfonated
Spherical polymer and the total weight ratio of sulfonating agent can be 1:1~1:9, such as 1:2~1:6, such as 1:3~1:5.
According to the present invention, the total weight of sulfonated spherical polymer and sulfonating agent can be 3:1~1:5, such as 2:1~
1:4。
According to the present invention, the temperature of the sulfonation procedure can change within a large range.
For example, when carrying out sulfonation before carbonization treatment, the temperature of sulfonation procedure can be 60-200 DEG C, such as 70-180
DEG C, for example, 80-150 DEG C；Sulfonation procedure can be reacted while heating within the said temperature range.
The speed of heating can be such as no more than 5 DEG C/min, to be such as no more than 3 DEG C/min no more than 10 DEG C/min.
According to the present invention, time of the sulfonation procedure can be 0.5-12 hours, preferably 1-10 hours, as 2-10 is small
When.
Preferably, the sulfonation carries out under inert gas atmosphere, and the inert gas can be selected from nitrogen, helium
One or more mixtures in gas, argon gas.
Wherein, in step 1), the spherical polymer is sulfonated polymer or not sulfonated polymer；Work as use
When not sulfonated polymer, it can carry out carrying out sulfonation in situ during sulfonation and/or carbonization treatment before carbonization treatment.
According to the present invention, the carbonization of step 1) can be in inert atmosphere or under the mixed atmosphere of inert gas and oxygen
It carries out.
In general, the temperature of the carbonization can be 100-650 DEG C, such as 150-600 DEG C.
When carrying out sulfonation before carburising step, the initial temperature of carburising step can be equal to or higher than sulfonation temperature
Exit temperature.
Preferably, carburising step can be reacted while heating within the said temperature range.The speed of heating can
Think and be no more than 10 DEG C/min, such as no more than 5 DEG C/min, is such as no more than 3 DEG C/min.
Preferably, the carbonization can successively be carried out in 2 or more temperature regions, such as in 2 to 10 temperature regions
It carries out successively.And preferably, the temperature of the temperature region is differing from each other.Alternatively, the temperature that carbonization can rise in gradient
Degree is lower to carry out.
Preferably, the carbonization can have in different temperatures region identical or different heating rate and it is identical or
Different soaking times.
Preferably, it when being carbonized when 2 or more temperature regions carry out successively, is carbonized first in the first temperature region,
Then next temperature region, such as the carbonization of second temperature region are sequentially entered；For example, the temperature of the first temperature region can be
100~400 DEG C, such as 150~350 DEG C；The temperature in second temperature region can be higher than the first temperature region, such as 400~650
DEG C, such as 450~650 DEG C.
Preferably, the carbonization time is -10 hours 30 minutes, such as 1-8 hours, such as 2-6 hours.
Preferably, the inert gas is selected from least one of nitrogen, helium, argon gas；
Preferably, when carbonization carries out under the mixed atmosphere of inert gas and oxygen, the volume of oxygen in mixed atmosphere
Percentage is 1-5%.
It should be appreciated that if the temperature residing for spherical polymer can both carry out sulfonation, spherical polymer can also be made to exist
Sulfonation in situ is carried out during carbonization.
According to the present invention, the activation of step 2) may include the first activation step and the second activation step.
Preferably, first activation step carries out in the atmosphere containing vapor；Second activation step containing
There is CO2Atmosphere in carry out.
Preferably, the temperature of the first time activation process is 700-1300 DEG C, such as 800-1200 DEG C, such as 850-950
℃；The time of first activation step can be 1-24 hours, such as 5-15 hours, such as 6-12 hours.
Preferably, the atmosphere of first activation step includes vapor, the especially mixing of vapor/inert gas
Object, the preferably mixture of vapor/nitrogen, or be made of above-mentioned.
Preferably, the volume ratio (velocity ratio) of the nitrogen and vapor is 3:1 or more, such as 4:1~10:1, preferably 4:
1~8:1.
According to the present invention, the atmosphere of first activation step can also include other gases, such as include oxidation carbons
(such as CO2), oxygen and ammonia etc..
Preferably, the temperature of second activation step is 700-1300 DEG C, preferably 800-1200 DEG C, for example, 850-
950℃；The time of second activation step is 1-10 hours, for example, 3-8 hours.
Preferably, the atmosphere of second activation step includes CO2, such as CO2Or CO2With the mixture of inert gas,
Such as CO2With the mixture of nitrogen.
Preferably, when second activation phenomenon includes nitrogen and CO2Mixture when, nitrogen and CO2Volume ratio (stream
Speed ratio) can be 10:1~1:10, such as 10:1~2:1, such as 8:1~4:1, such as 3:1~2:1.
According to the present invention, the atmosphere of second activation step can not include other gases, such as not comprising vapor.
According to the present invention, heating can use gradient increased temperature.Alternatively, 1 can be stopped when being warming up to certain temperature
~240min, such as 5~150min, then heat up again.
Preferably, the temperature-rise period of the method for the present invention can be accomplished continuously or intermittently.
According to the present invention, in step 3), the temperature of the acidification is 0~60 DEG C, such as 10-50 DEG C, such as 20-40 DEG C.
According to the present invention, in step 3), time of the acidification can be 0.5-12 hours, preferably 1-10 hours,
Such as 3-6 hours.
According to the present invention, in step 3), the mass volume ratio of product and nitric acid that step 2) obtains is 1g：(5~30) mL,
For example, 1g：(8~25) mL, such as 1g：(10~20) mL.
According to the present invention, in step 3), the nitric acid is aqueous solution of nitric acid, and mass fraction is 15~75%, such as 20
~70%.
The present invention also provides activated carbons prepared by method as described above.
Purposes the present invention also provides the activated carbon as adsorbent.
Preferably, the activated carbon is used as being adsorbed in water when adsorbent.
Beneficial effects of the present invention：
The present invention provides a kind of methods improving activated carbon adsorption performance；What method through the invention can make
Activated carbon has water-compatible appropriate, while modified water-compatible, while in water metallic element or be dissolved in water
Organic matter etc. has good absorption property.
The activated carbon that the present invention is prepared may be implemented to such as Li, Na of the metallic element in water phase, K, Ca, Mg, Ba,
Cu, Zn, Si, Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cd, Hg, Pb, Pt, La, Re, Sn, Sb, P, Al etc. or organic matter such as benzene
Effective absorption of phenol, methylphenol, nitrobenzene and aniline, and with preferable selectivity；The activated carbon is in preparation process
Simple for process, which not only saves cost, compared to the activated carbon after activation, to the adsorption capacity of metallic element
It is stronger.
Specific implementation mode
Further detailed description is done to technical scheme of the present invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on the above of the present invention are encompassed by the present invention is directed to protect.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1
The preparation of 1.1 spherical polymers
Under protection of argon gas, in equipped with churned mechanically 250mL three-necked flasks, by 0.020mol 2,2 bis- (fluoroforms
Base) benzidine is added into 20mL DMF, after stirring makes raw material be completely dissolved, then 0.016mol is added into reaction system
After reacting 5h, 0.0008mol norbornene acid anhydrides is added, the reaction was continued, and 20h obtains polyamic acid solution in biphenyl dianhydride.
Using 3.62g triethylamines as catalyst, catalyst is added in polyamic acid solution, and 14.6g dehydrating agents are added
Acetic anhydride, the reaction was continued 20h obtain polyimide prepolymer solution, then by polyimide prepolymer solution polar solvent N-
Methyl pyrrolidone carries out after diluting in equal volume, instills in methanol precipitated dropwise, and by washing of precipitate and filtering, repetition is washed
It washs, 10h or more is dried under 60 DEG C of vacuum in it, obtains polyimide prepolymer powder.
3.10g polyimide prepolymer powder is dissolved in 4.8g N-Methyl pyrrolidones, it is 40% to obtain solid content
Performed polymer glue, then into performed polymer glue be added 0.055g radical initiator AIBN, obtain mixed glue solution, free radical
The quality of initiator and the mass ratio of polyimide prepolymer are about 1:28, after its dissolving, mixed glue solution is filled by being granulated
It sets and prepares spherical polymer, be then placed in high temperature drying baking oven and cured, solidification process is：Cure 1.5h at 40 DEG C,
Cure 1.5h at 65 DEG C, cure 1h at 120 DEG C, after curing 1.5h at 170 DEG C after naturally cool to room temperature, by it from glass
It is stripped down in glass plate, polymer polyimide.
1.2 sulfonation and carbonization
It is 1 by mass ratio:The spherical polymer that 8 step 1.1 obtains is mixed with the concentrated sulfuric acid, is then fed the mixture into resistance to
Sour rotary tube furnace carries out following sulfonation processing with the heating speed of 4 DEG C/min in a nitrogen atmosphere：
60 DEG C are heated to, is stopped 80 minutes；
130 DEG C are heated to, is stopped 120 minutes；
150 DEG C are heated to, is stopped 120 minutes；
Continue to heat up with the heating speed of 5 DEG C/min, and in the mixed atmosphere that the percent by volume of oxygen is 3%, into
Row carbonization treatment：
350 DEG C are heated to, is stopped 240 minutes；
530 DEG C are heated to, is stopped 120 minutes.Cooling, obtains carbonized product.
1.3 activation
In rotary tube furnace, volume ratio 1:Under the water vapour of 5 (L/min) and the mixed atmosphere of nitrogen, by step 1.2
Obtained carbonized product is heated to 750 DEG C with the speed of 4 DEG C/min, after stopping 280min, then in velocity ratio is 1:5.5(L/
Min under the mixed atmosphere of carbon dioxide and nitrogen), 950 DEG C is heated to the speed of 3 DEG C/min, stops 250min.Cooling,
Obtain activation products 18.9g.
1.4 acidification
It is in 60% aqueous solution of nitric acid, at 40 DEG C that the product (18.9g) that step 1.3 obtains, which is placed in 189mL mass fractions,
Processing 3 hours, washing are dried to obtain activated carbon WSC1, and yield is with polymer weight for 49%.
Embodiment 2
2.1 steps are the same as 1.1 in embodiment 1.
2.2 sulfonation and carbonization
Sulfonation processing is carried out to the spherical polymer of step 2.1, then by mass ratio is 1:That treated is spherical poly- for 5 sulfonation
It closes object to mix with the concentrated sulfuric acid, acidproof rotary tube furnace is then fed the mixture into, in a nitrogen atmosphere, with the heating of 3 DEG C/min
Speed carries out following sulfonation processing：
60 DEG C are heated to, is stopped 60 minutes；
110 DEG C are heated to, is stopped 100 minutes；
140 DEG C are heated to, is stopped 240 minutes；
Continue to heat up with the heating speed of 4 DEG C/min again, and in the mixed atmosphere that the percent by volume of oxygen is 3%,
Carry out carbonization treatment：
360 DEG C are heated to, is stopped 360 minutes；
540 DEG C are heated to, is stopped 240 minutes.Cooling, obtains carbonized product.
2.3 activation
In rotary tube furnace, volume ratio 1:Under the water vapour of 5.5 (L/min) and the mixed atmosphere of nitrogen, by step
2.2 obtained carbonized products are heated to 750 DEG C with the speed of 3 DEG C/min, after stopping 300min, then in velocity ratio are 1:4.5(L/
Min under the mixed atmosphere of carbon dioxide and nitrogen), 900 DEG C is heated to the speed of 3 DEG C/min, stops 300min.Cooling,
Obtain activation products 15.6g.
2.4 acidification
It is in 30% aqueous solution of nitric acid, at 30 DEG C that the product (15.6g) that step 2.3 obtains, which is placed in 312mL mass fractions,
Processing 5 hours, washing are dried to obtain activated carbon WSC2, and yield is with polymer weight for 42%.
Embodiment 3
3.1 steps are the same as 1.1 in embodiment 1
3.2 sulfonation and carbonization
Sulfonation processing is carried out to the spherical polymer of step 3.1, then by mass ratio is 1:That treated is spherical poly- for 3 sulfonation
It closes object to mix with the concentrated sulfuric acid, acidproof rotary tube furnace is then fed the mixture into, in a nitrogen atmosphere, with the heating of 2 DEG C/min
Speed carries out following sulfonation processing：
60 DEG C are heated to, is stopped 60 minutes；
110 DEG C are heated to, is stopped 120 minutes；
150 DEG C are heated to, is stopped 200 minutes；
Continue to heat up with the heating speed of 3 DEG C/min, and in the mixed atmosphere that the percent by volume of oxygen is 3%, into
Row carbonization treatment：
320 DEG C are heated to, is stopped 240 minutes；
520 DEG C are heated to, is stopped 240 minutes.Cooling, obtains carbonized product.
3.3 activation
In rotary tube furnace, volume ratio 1:Under the water vapour of 5 (L/min) and the mixed atmosphere of nitrogen, by step 3.2
Obtained carbonized product is heated to 750 DEG C with the speed of 3 DEG C/min, after stopping 240min, then in velocity ratio is 1:4.5(L/
Min under the mixed atmosphere of carbon dioxide and nitrogen), 900 DEG C is heated to the speed of 3 DEG C/min, stops 240min, is cooled down,
Obtain activation products 16.7g.
3.4 acidification
It is in 50% aqueous solution of nitric acid, at 20 DEG C that the product (16.7g) that step 3.3 obtains, which is placed in 250mL mass fractions,
Processing 6 hours, washing are dried to obtain activated carbon WSC3, and yield is with polymer weight for 46%.Comparative example 1
The operation of this comparative example is identical as 1 1.1-1.3 operations of embodiment, the difference is that without 1.4 acidifications.
Comparative example 2
The operation of this comparative example is identical as 1 1.1-1.3 operations of embodiment, the difference is that the temperature of step 1.4 acidification is
80℃。
Comparative example 3
The operation of this comparative example is with 1 1.1-1.3 operations of embodiment identical, the difference is that step 1.4 acidification uses
Nitric acid mass fraction is 10%.
Embodiment 4
Example 1 respectively, activated carbon 5g prepared by comparative example 1~3, is added to dissolved with 3gFeCl3100mL water in
It is impregnated, dipping temperature is 80 DEG C, dip time 12h.After the completion of dipping, activated carbon is taken out, is dried at room temperature, calculated
The weightening of activated carbon.
| Sample | Gain in weight (g) |
| Embodiment 1 | 2.88 |
| Comparative example 1 | 0.12 |
| Comparative example 2 | 1.60 |
| Comparative example 3 | 0.90 |
From the above results, the active product char water-compatible that the present processes obtain is good, can be to soluble in water
FeCl3It is adsorbed well, activated carbon of the comparative example 1 without acidification, since its water-compatible is poor, then in water
The absorption of metallic element it is less.And comparative example 2 and 3 adsorption activities are also inferior to 1 product of embodiment.Therefore, the present processes
Obtained product water-compatible is obviously improved.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiments.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of method improving activated carbon adsorption performance, which is characterized in that include the following steps：
1) spherical polymer is subjected to sulfonation and carbonization treatment；
2) product for obtaining step 1) carries out activation process；
3) acidification is carried out using nitric acid to the product that step 2) obtains.
2. according to the method described in claim 1, it is characterized in that, in step 1), the polymer is by by monomer, initiator
Mixing carries out polymerisation preparation；
The polymer matrix of the copolymer includes the structural unit derived from the first monomer and the structure derived from second comonomer
Unit, wherein first monomer have 2~10 carbon atoms and contain at least two amino, the second comonomer have 4~
15 carbon atoms and contain at least two carboxyls or at least one acid anhydrides；
Preferably, in step 1), the spherical polymer be selected from polyimides, the polyimides be aliphatic polyimide,
At least one of semi-aromatic polyimides and aromatic polyimide；
Preferably, the spherical polymer can be unsulfonated or the polymer of sulfonation；
Preferably, the sulfonation is to carry out not sulfonated spherical polymer and sulfonating agent；And/or by sulfonated ball
Shape polymer is carried out with sulfonating agent.
3. method according to claim 1 or 2, which is characterized in that in step 1), the spherical polymer is sulfonated
Polymer or not sulfonated polymer；When using not sulfonated polymer, sulfonation and/or carbon are carried out before carbonization treatment
Change and carries out sulfonation in situ in processing procedure.
4. according to claim 1-3 any one of them methods, which is characterized in that the carbonization of step 1) inert atmosphere or
It is carried out under the mixed atmosphere of inert gas and oxygen；
Preferably, the temperature of the carbonization is 100-650 DEG C；
Preferably, when carrying out sulfonation before carburising step, the initial temperature of carburising step is equal to or higher than sulfonation temperature
Exit temperature.
5. according to claim 1-4 any one of them methods, which is characterized in that the activation of step 2) includes the first activation step
With the second activation step；
Preferably, first activation step carries out in the atmosphere containing vapor；Second activation step is containing CO2
Atmosphere in carry out；
Preferably, the temperature of the first time activation process is 700-1300 DEG C；The time of first activation step is 1-24
Hour；
Preferably, the temperature of second activation step is 700-1300 DEG C；The time of second activation step is that 1-10 is small
When；
Preferably, the atmosphere of second activation step includes CO2。
6. according to claim 1-5 any one of them methods, which is characterized in that in step 3), the temperature of the acidification
It is 0~60 DEG C；
Preferably, in step 3), the time of the acidification is 0.5-12 hours.
7. according to claim 1-6 any one of them methods, which is characterized in that in step 3), product that step 2) obtains with
The mass volume ratio of nitric acid is 1g：(5~30) mL；
Preferably, in step 3), the nitric acid is aqueous solution of nitric acid, and mass fraction is 15~75%.
8. the activated carbon prepared according to claim 1-7 any one of them methods.
9. the purposes of activated carbon prepared by claim 1-7 any one of them methods as adsorbent.
10. purposes according to claim 9, which is characterized in that the activated carbon is used as being inhaled in water when adsorbent
It is attached.
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| CN111359581A (en) * | 2020-02-19 | 2020-07-03 | 东华大学 | Method for preparing heavy metal adsorbent by using waste polyvinyl chloride plastic |
| CN113842877A (en) * | 2021-09-24 | 2021-12-28 | 中国科学院青海盐湖研究所 | Carbon-based adsorbent particle for extracting liquid lithium resource, preparation method and preparation device |
| CN116099500A (en) * | 2023-02-10 | 2023-05-12 | 北方民族大学 | Sulfur-doped carbon material, preparation method and application thereof |
| CN116371377A (en) * | 2023-03-30 | 2023-07-04 | 常州大学 | Composite porous adsorption material for volatile organic compounds and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111359581A (en) * | 2020-02-19 | 2020-07-03 | 东华大学 | Method for preparing heavy metal adsorbent by using waste polyvinyl chloride plastic |
| CN111359581B (en) * | 2020-02-19 | 2021-08-17 | 东华大学 | Method for preparing heavy metal adsorbent by using waste polyvinyl chloride plastic |
| CN113842877A (en) * | 2021-09-24 | 2021-12-28 | 中国科学院青海盐湖研究所 | Carbon-based adsorbent particle for extracting liquid lithium resource, preparation method and preparation device |
| CN113842877B (en) * | 2021-09-24 | 2023-09-22 | 中国科学院青海盐湖研究所 | Carbon-based adsorbent particles for liquid lithium resource extraction, preparation method and preparation device |
| CN116099500A (en) * | 2023-02-10 | 2023-05-12 | 北方民族大学 | Sulfur-doped carbon material, preparation method and application thereof |
| CN116371377A (en) * | 2023-03-30 | 2023-07-04 | 常州大学 | Composite porous adsorption material for volatile organic compounds and preparation method thereof |
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