CN110734065B - Method for recycling super-capacity carbon - Google Patents

Method for recycling super-capacity carbon Download PDF

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CN110734065B
CN110734065B CN201810799401.6A CN201810799401A CN110734065B CN 110734065 B CN110734065 B CN 110734065B CN 201810799401 A CN201810799401 A CN 201810799401A CN 110734065 B CN110734065 B CN 110734065B
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carbonization
carbon
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CN110734065A (en
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常明珠
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Shenzhen Global Greenland New Materials Co ltd
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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
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • C01B32/36—Reactivation or regeneration
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • 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
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • C01B32/378—Purification
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Carbon And Carbon Compounds (AREA)

Abstract

The invention belongs to the technical field of super-capacity carbon, and particularly relates to a method for recycling super-capacity carbon. The method comprises the following steps: s1) collecting the scrapped super capacitor, and obtaining electrode plates in the super capacitor; s2) pulverizing or grinding the electrode sheet obtained in step S1); s3) sieving the crushed or ground substance obtained in the step S2) by a sieve of 200 meshes and 1000 meshes to obtain powder, and simultaneously separating aluminum foil; s4) mixing the powder obtained in the step S3) with an organic solvent or a mixed solution of the organic solvent and water, and separating to obtain a suspension; s5) carrying out centrifugal filtration on the suspension obtained in the step S4) to obtain powder, soaking the powder in an acid solution under the condition of microwave irradiation, and drying. The method can well recover the super-capacity carbon product in the waste super capacitor, and the obtained product can still be used as an adsorbent to adsorb harmful gas, thereby achieving the purpose of changing waste into valuable.

Description

Method for recycling super-capacity carbon
Technical Field
The invention belongs to the technical field of super-capacity carbon, and particularly relates to a method for recycling super-capacity carbon.
Background
A supercapacitor is a new type of energy storage device between a conventional capacitor and a secondary battery, and its capacity can reach several hundred or even thousands of farads. Compared with the traditional capacitor, the capacitor has higher energy density, larger capacity, wider working temperature range and better service life; compared with secondary batteries, it has higher power density and longer cycle life, and no environmental pollution. Due to excellent energy density, power density and cycle service life, the super capacitor is widely applied to the fields of electronic toys, information products, household appliances, electric tools, electric automobiles, weaponry, aerospace, electric power energy storage and the like.
The carbon-based material has the characteristics of porosity, high specific surface area, high porosity, good chemical stability, long service life and the like, and is often used as an electrode material of an electric double layer capacitor, so that higher energy density and power density can be obtained.
The ultracapacitors can maintain an ultra-long service life and do not fail despite operating within specified operating parameters. The service life of a supercapacitor can exceed most other electronic components in any given application, which is why supercapacitors are the best means of power transmission in harsh environments. However, in practical applications, such as in the use of power vehicles, a large amount of discarded supercapacitors may be generated. Generally, although the super-capacity carbon in the discarded super-capacitor can be recovered by a certain method, the recovered super-capacity carbon is difficult to be reused as an electrode material, or even if the super-capacity carbon can be used as other products (such as an adsorbent), the performance is low, and the use requirement cannot be met.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for recycling ultra-volume carbon, which comprises the following steps:
s1) collecting the scrapped super capacitor containing the activated carbon, and obtaining electrode plates in the super capacitor;
s2) pulverizing or grinding the electrode sheet obtained in step S1);
s3) sieving the crushed or ground substance obtained in the step S2) by a sieve of 200 meshes and 1000 meshes to obtain powder, and simultaneously separating aluminum foil;
s4) mixing the powder obtained in the step S3) with an organic solvent or a mixed solution of the organic solvent and water, and separating to obtain a suspension;
s5) carrying out centrifugal filtration on the suspension obtained in the step S4) to obtain powder, soaking the powder in an acid solution under the condition of microwave irradiation, and drying to realize the recovery of the super-capacity carbon.
According to the present invention, in step S1), the activated carbon in the supercapacitor may be prepared by the following method:
1) carbonizing the spherical polymer;
2) pre-activating the product obtained in the step 1);
3) cooling the product obtained by pre-activation in the step 2), mixing the product with an alkaline compound, and activating.
According to the present invention, in step 1), the polymer may be prepared by mixing a monomer and an initiator to perform a polymerization reaction.
By way of example, the polymer may be a homopolymer or a copolymer. Wherein, the homopolymer refers to a polymer prepared by polymerizing one monomer, and the copolymer refers to a polymer prepared by polymerizing two or more monomers.
According to the invention, the monomer can be selected from compounds having 2 to 60 carbon atoms and having at least 1 carbon-carbon double bond, for example compounds having 2 to 20 carbon atoms and having at least 1 carbon-carbon double bond. For example, the monomer may be selected from the following: ethylene, propylene, isopropene, butene, isobutylene, pentene, isopentene, neopentene, hexene, isohexene, neohexene, styrene, methylstyrene, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butadiene, pentadiene, isoprene, pentadiene, isohexadiene, divinylbenzene, diethylene glycol divinyl ether.
Alternatively, the polymer matrix of the copolymer comprises structural units derived from a first monomer having from 2 to 10 carbon atoms and containing at least one carbon-carbon double bond and structural units derived from a second monomer having from 4 to 15 carbon atoms and containing at least two carbon-carbon double bonds.
Preferably, in the polymer matrix of the copolymer, the structural units derived from the first monomer constitute from 75% to 98%, preferably from 80% to 90%, of the total structural units of the polymer network; the structural units derived from the second monomer constitute from 25% to 2%, preferably from 20% to 10%, of the total structural units of the polymer network.
According to the invention, the first monomer is selected from one or more of styrene, methyl styrene, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate and mono-olefin with 2-6 carbon atoms, such as ethylene, propylene, isopropene, butene, isobutene, pentene, isopentene, neopentene, hexene, isohexene, neohexene and the like.
According to the invention, the second monomer is selected from one or more of butadiene, pentadiene, isoprene, pentadiene, isohexadiene, divinylbenzene and diethylene glycol divinyl ether.
According to the invention, the polymerization reaction may be a suspension polymerization reaction; preferably, the polymerization is also carried out in the presence of water, dispersants, dispersion aids.
For example, water: dispersing agent: the weight ratio of the auxiliary dispersing agent is 800-1000: 0.5-3.0: 0.05 to 0.2;
when the polymer is a homopolymer, the monomer: the weight ratio of the initiator may be 1: 0.003 to 0.01.
First monomer, if present: a second monomer: the weight ratio of the initiator can be 0.75-0.98: 0.02-0.25: 0.003 to 0.01.
Preferably, the water, the dispersant and the co-dispersant constitute a water phase, and the monomer of the homopolymer, the first monomer of the copolymer, the second monomer and/or the initiator constitute an oil phase; the weight ratio of the oil phase to the water phase can be 1: 4-6.
According to the present invention, the suspension polymerization reaction may comprise:
adding the components into a reaction kettle, introducing compressed air or nitrogen into the reaction kettle, keeping the pressure in the reaction kettle in a positive pressure state with the gauge pressure less than or equal to 0.5MPa, heating to 70-90 ℃, preserving heat for 2-24 hours, heating to 100-150 ℃, preserving heat for 4-36 hours, then washing with water, drying and screening to obtain the spherical polymer.
In a preferred embodiment, the dispersant is an inorganic dispersant such as a silicate, carbonate or phosphate, or a combination thereof, or an organic dispersant such as polyvinyl alcohol, gelatin, carboxymethyl cellulose or polyacrylate, or a combination thereof.
In a preferred embodiment, the co-dispersant is sodium lauryl sulfate, calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, calcium petroleum sulfonate, sodium petroleum sulfonate or barium stearate, or a combination thereof.
In a preferred embodiment, the initiator is an organic peroxide compound, an inorganic peroxide compound or an azo compound, or a combination thereof.
In preferred embodiments, the initiator is a diacyl peroxide, a dioxane peroxide, a peroxyester, azobisisobutyronitrile, or a persulfate, or a combination thereof.
Preferably, the polymerization reaction may also be carried out in the presence of a porogen. The porogen may be selected from paraffin, magnesium sulfate, sodium carbonate, gelatin or glycerol, or a combination thereof.
According to the invention, the spherical polymer has a median particle diameter D50It may be 0.1 to 2.0mm, for example, 0.3 to 1.8mm, specifically, 0.8mm, 0.9mm, 1.0mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7 mm.
According to the invention, the polymer may be a sulfonated polymer or a non-sulfonated polymer. When non-sulfonated polymers are used, sulfonation may be performed prior to the carbonization step and/or sulfonation may be performed in situ during carbonization.
By way of example, the unsulfonated polymers may also be prepared according to known methods or commercially available.
The sulfonation can be carried out using starting materials known in the art, for example, by contacting the unsulfonated polymer with a sulfonating agent. The sulfonating agent may be selected from sulfuric acid (e.g., concentrated sulfuric acid), oleum, SO3A mixture of one or more of them.
According to the invention, the total weight ratio of the non-sulfonated spherical polymer to the sulfonating agent may be 3:1 to 1:3, for example 2:1 to 1:2, such as 1:1 to 1: 1.5.
The temperature of the sulfonation step may vary over a wide range.
For example, when sulfonation is carried out prior to the carbonization step, the temperature of the sulfonation step may be 60 to 200 ℃, such as 70 to 180 ℃, for example 80 to 150 ℃;
preferably, the sulfonation step may be carried out while raising the temperature within the above-mentioned temperature range. The rate of temperature rise may be no more than 10 deg.C/min, for example no more than 5 deg.C/min, such as no more than 3 deg.C/min.
The time of the sulfonation step may be from 0.5 to 12 hours, preferably from 1 to 10 hours, such as from 2 to 10 hours.
Preferably, the sulfonation is carried out under an inert gas atmosphere, which may be selected from a mixture of one or more of nitrogen, helium, and argon.
According to the present invention, the carbonization in step 1) may be performed in an inert atmosphere or in a mixed atmosphere of an inert gas and oxygen.
Typically, the temperature of the carbonization may be 100-950 ℃, such as 150-900 ℃, such as 300-850 ℃.
When sulfonation is performed prior to the carbonization step, the starting temperature of the carbonization step may be equal to or higher than the ending temperature of the sulfonation temperature.
Preferably, the carbonization step may be carried out while raising the temperature within the above-mentioned temperature range. The rate of temperature rise may be no more than 10 deg.C/min, for example no more than 5 deg.C/min, such as no more than 3 deg.C/min.
Preferably, the carbonization may be performed sequentially in 2 or more temperature zones, for example, sequentially in 2 to 10 temperature zones. And preferably, the temperatures of the temperature regions are different from each other. Alternatively, carbonization may be carried out at a gradient of increasing temperature.
Preferably, the carbonization may have the same or different temperature rise rates and the same or different holding times in different temperature regions.
Preferably, when carbonization is sequentially performed in 2 or more temperature zones, carbonization is first performed in a first temperature zone, and then carbonization is sequentially performed in a next temperature zone, for example, a second temperature zone; for example, the temperature of the first temperature region may be 100 to 500 ℃, for example, 150 to 450 ℃; the temperature of the second temperature zone may be higher than the first temperature zone, for example 500 to 950 ℃, such as 650 to 950 ℃.
Preferably, the carbonization time is from 30 minutes to 10 hours, for example from 1 to 8 hours, such as from 2 to 6 hours.
Preferably, the inert gas is selected from at least one of nitrogen, helium, argon;
preferably, when the carbonization is performed under a mixed atmosphere of an inert gas and oxygen, the volume percentage of oxygen in the mixed atmosphere is 1 to 5%.
It will be appreciated that if the spherical polymer is subjected to temperatures that allow sulfonation, the spherical polymer may also be sulfonated in situ during carbonization.
According to the invention, the preactivation of step 2) is carried out in an atmosphere comprising water vapor and/or carbon dioxide.
Preferably, the temperature of the pre-activation treatment is 700-1300 ℃, such as 800-1200 ℃, such as 850-950 ℃; the time for the pre-activation step may be from 1 to 24 hours, for example from 5 to 15 hours, such as from 6 to 12 hours.
Preferably, the atmosphere of the pre-activation step comprises water vapour, in particular water vapour and/or carbon dioxide, and a mixture of inert gases, preferably water vapour and/or carbon dioxide, nitrogen.
Preferably, the volume ratio (flow rate ratio) of the nitrogen gas, the water vapor and the carbon dioxide is 3:1:1 or more, for example, 3 to 10:1:1, preferably 4 to 8:1: 1.
According to the invention, the basic compound used in step 3) can be chosen from organic or inorganic bases chosen from hydroxides, carbonates or bicarbonates of alkali or alkaline earth metals, such as LiOH, NaOH, KOH, Ca (OH)2、Na2CO3、NaHCO3、K2CO3One, two or more.
Alternatively, the basic compound may also be an oxide of an alkali metal or an oxide of an alkaline earth metal, such as CaO, K2O、Li2O or mixtures thereof.
According to the invention, the mass ratio of the product obtained in the step 2) in the step 3) to the alkaline compound is 1 (1-5), and preferably 1 (3-4).
Preferably, the temperature of the activation step is 700-1300 ℃, preferably 800-1200 ℃, for example 850-950 ℃; the time for the activation step is 1 to 10 hours, for example 3 to 8 hours.
Preferably, the atmosphere of the activation step is selected from an atmosphere containing no oxygen.
For example, the atmosphere of the activation step is selected from CO2Or CO2Mixtures with inert gases, e.g. CO2And nitrogen.
Preferably, when the activating atmosphere comprises nitrogen and CO2In the mixture of (1), nitrogen and CO2The volume ratio (flow rate ratio) of (a) may be 10:1 to 1:10, such as 10:1 to 2:1, for example 8:1 to 4:1, such as 3:1 to 2: 1.
According to the present invention, the temperature rise may use a gradient temperature rise. Alternatively, the temperature may be raised to a certain temperature, and then the temperature may be raised again after the temperature is raised to 1 to 240min, for example, 5 to 150 min.
Preferably, the temperature increase process of the present invention may be continuous or intermittent.
According to the invention, in step S4), the powder material and the organic solvent or the mixed solution of the organic solvent and water are mixed and soaked for a period of time, such as 5h, to fully dissolve the powder material. The soaking is preferably vacuum soaking. The organic solvent is preferably methanol, ethanol, acetone, ethyl acetate, chloroform, or the like.
According to the invention, before the step S4), the powder obtained in the step S3) is treated to remove conductive carbon and binder impurities contained in the powder; the processing method comprises the following steps: the powder is mixed with an inorganic base such as sodium hydroxide or potassium hydroxide, and then centrifuged and filtered. Preferably, the powder obtained by the centrifugal separation and filtration is washed with deionized water and dried at room temperature. The concentration of the sodium hydroxide or potassium hydroxide is preferably 5 to 30 wt%.
According to the invention, in step S5), the acidic solution is at least one selected from hydrochloric acid, nitric acid and sulfuric acid; preferably, sulfuric acid is used. The concentration of the acidic solution is not particularly limited, and oxidation and ablation treatment of the surface of the activated carbon, particularly the pore structure can be achieved, and the concentration of the acidic solution is 3 to 20wt% for example; for example 8-15 wt%.
According to the invention, the mass-to-volume ratio of the powder to the acidic solution is 1: 15-30; for example, 1: 15-25.
According to the present invention, the temperature of the recovery is not particularly limited, and may be set according to the temperature to which the energy provided by the microwave irradiation is converted, and the temperature is preferably 30 ℃ or more; the recovery time is preferably from 4 to 16 hours, for example from 6 to 10 hours, such as 8 hours.
According to the invention, under the microwave irradiation condition, the wavelength of the microwave is between 1m and 1000nm, and the frequency is 300MHz to 300 GHz. The power of the microwave irradiation is 200-800W.
Advantageous effects
The application provides a method for recycling the super-capacity carbon, the method is simple to operate, the original super-capacity carbon can be recycled with high yield, and the super-capacity carbon obtained by treatment can be further used as an adsorbent to adsorb toxic and harmful gases, such as CO and H2S、HCl、SO2、NOXAmmonia, benzene, formaldehyde. And still maintain a good adsorption capacity. The method is simple to operate, has practical application value and is suitable for popularization.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples are all commercially available products or can be prepared by known methods (e.g., literature report methods). The specific surface areas in the examples were measured by a nitrogen physisorption instrument model Belsorp mini II from microtrac bel corp.
Preparation example 1
Adding 20 liters of water into a 50 liter polymerization kettle, heating to 30 ℃, respectively adding 11.5g of magnesium carbonate, 25g of gelatin and 0.20g of methylene blue under the stirring state, stirring uniformly, adding an oil phase formed by mixing 3.5kg of methyl styrene, 1.2kg of dipentene and 24g of benzoyl peroxide, adding 1.2kg of paraffin, sealing the polymerization kettle, introducing clean compressed air into the polymerization kettle, and keeping the gas phase pressure in the kettle at 0.05 MPa. Then, starting stirring, adjusting the liquid beads in the kettle to proper particle size, heating to 80 ℃, preserving heat for 12 hours, heating to 110 ℃, preserving heat for 24 hours, filtering and washingWashing, drying and sieving to obtain 2.54kg of white spherical polymer, and detecting that the BET of the product is 10.568m2/g。
1.1 carbonization
2kg of median particle diameter D50The white spherical polymer having a particle size of 0.8mm was charged into a rotary tube furnace, and subjected to the following heat treatment at a heating rate of 4 ℃/min under a nitrogen atmosphere:
heating to 100 deg.C, and standing for 100 min;
heating to 150 ℃, and staying for 200 minutes;
the following heat treatment was carried out at a heating rate of 5 ℃/min:
heating to 350 deg.C, and standing for 100 min;
heating to 500 deg.C, and standing for 200 min;
then heated to 650 ℃ and left for 100 minutes. And cooling to obtain 1.76kg of carbonized product.
1.2 Pre-activation and activation
In a rotating tube furnace, the carbonized product obtained in the step 1.1 is heated to 950 ℃ at the speed of 4 ℃/min under the mixed atmosphere of water vapor, carbon dioxide and nitrogen with the flow rate ratio of 1:1:4.5(L/min), stays for 360min, is heated to 1000 ℃ at the speed of 3 ℃/min, and stays for 240 min. Cooling, adding 7kg KOH, heating to 700 ℃ at the speed of 3 ℃/min, staying for 250min, and cooling to obtain the spherical super-capacity carbon, wherein the yield is 36% by polymer. The detection proves that the specific surface area of the product is 2679m2(ii)/g, bulk density of 0.259g/mL, average pore volume of 2.473cm3In terms of/g, the mean pore diameter was 3.316 nm.
Mixing 500g of prepared spherical super-capacity carbon with conductive carbon black and PTFE according to the mass ratio of 9:2:1, adding water, uniformly stirring to obtain slurry, coating the slurry on the surface of a conductive aluminum foil through a coating machine, and drying to obtain an electrode;
rolling, cutting and punching the electrode to obtain a semi-finished product of the electrode plate of the super capacitor with the electrode thickness of 200 mu m, the length of 75mm and the width of 55mm, and then drying the semi-finished product in a vacuum drying oven at 120 ℃ for 12 hours to obtain a finished product of the electrode plate;
cellulose paper is used as a diaphragm, 2 supercapacitor electrode plates with equal mass are oppositely placed, and then acetonitrile solution of 1.0M TEABF4 is used as electrolyte to assemble the supercapacitor. The capacitor is continuously charged and discharged until the capacitor is scrapped.
Example 1
The super capacitor in preparation example 1 was disassembled, and the electrode sheet case was taken out and recovered according to the classification of aluminum case, steel case, plastic, etc. Cut into 20mm2Grinding the large and small pole pieces in a grinder until the pole pieces are ground into powder, pouring the powder into a 300-mesh screen, placing a large container below the 300-mesh screen to enable the powder to fall into the container after being screened, and separating out the aluminum foil; adding 15 wt% of potassium hydroxide into the powder, stirring and soaking, centrifugally separating and filtering the obtained mixed solution, washing with deionized water for multiple times, and drying at room temperature. Then, the powder is soaked in an ethanol solvent at room temperature, stirred for 30min, separated to obtain a suspension, and then the obtained suspension is subjected to centrifugal filtration to obtain 516g of powder.
516g of powder is immersed in 10 wt% hydrochloric acid solution for 12 hours at 40 ℃ under the microwave irradiation condition with the power of 600W, and is filtered and dried to obtain 448g of activated carbon product. The yield was 89.6% calculated on the basis of the spherical activated carbon as the raw material for preparing the super-capacity carbon.
And (3) taking the obtained activated carbon product as an adsorbent to carry out a test on the removal rate of the gaseous pollutants, wherein the test method comprises the following steps:
weighing 100 g of a sample to be tested, paving the sample on a tray, vertically placing a glass rod wound with 5 layers of gauze into a 500mL reagent bottle, filling 200mL of pollutants formaldehyde (0.2%), ammonia (1%), benzene (0.06%), TVOC (0.06%, toluene 0.1% and xylene 0.4%), and attaching a mark A1. The tray without the sample is placed in the blank test chamber A, and the tray with the sample is placed in the sample test chamber B. Releasing source A1Put into the blank test chamber A and the sample test chamber B, and immediately close the chamber door. And turning on fans of the A cabin and the B cabin to stir for 1 minute, and keeping the circulating fan on or off according to the requirement of the test conditions. After 24 hours, respectively carrying out sample collection test analysis on the A cabin and the B cabin, and respectively recording the concentrations as CAAnd CB。
The calculation method of the removal rate y (%) comprises the following steps:
y(％)＝(CA–CB)/CA×100
wherein C isAIs the blank cell concentration, CBIs the test chamber concentration.
It is found by calculation that the sample of example 1 has a formaldehyde removal rate of 68.8%, an ammonia removal rate of 59.2%, and a TVOC removal rate of 43.6%.
From the results, the method of the invention can well activate and reprocess the super-capacity carbon product in the waste super capacitor, and the obtained product can still be used as an adsorbent to adsorb harmful gas. Therefore, the method can achieve the purpose of changing waste into valuable.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (12)

1. A method for recycling ultra-volume carbon, which is characterized by comprising the following steps:
s1) collecting the scrapped super capacitor containing the activated carbon, and obtaining electrode plates in the super capacitor;
s2) pulverizing or grinding the electrode sheet obtained in step S1);
s3) sieving the crushed or ground substance obtained in the step S2) by a sieve of 200 meshes and 1000 meshes to obtain powder, and simultaneously separating aluminum foil;
s4) mixing the powder obtained in the step S3) with an organic solvent or a mixed solution of the organic solvent and water, and separating to obtain a suspension;
s5) carrying out centrifugal filtration on the suspension obtained in the step S4) to obtain powder, soaking the powder in an acid solution under the condition of microwave irradiation, and drying to realize recovery of the super-capacity carbon;
the active carbon in the super capacitor is prepared by the following method:
1) carbonizing the spherical polymer;
2) pre-activating the product obtained in the step 1);
3) mixing the product obtained by the pre-activation in the step 2) with an alkaline compound and then activating;
the polymer is a sulfonated polymer or an unsulfonated polymer; when non-sulfonated polymers are used, sulfonation is carried out in situ during sulfonation and/or carbonization prior to the carbonization step;
the carbonization in the step 1) is carried out in the mixed atmosphere of inert gas and oxygen;
when carbonization is carried out in 2 temperature areas in sequence, firstly, carbonization is carried out in a first temperature area, and then carbonization is carried out in a second temperature area; the temperature of the first temperature area is 100-500 ℃; the temperature of the second temperature region is 500-650 ℃.
2. The method of claim 1, wherein in step S4), the powder is mixed with the organic solvent or the mixed solution of the organic solvent and water and then soaked for a period of time, such that the powder is fully dissolved, and the soaking time is 5 hours.
3. The method of claim 2, wherein the soaking is vacuum soaking.
4. The method according to claim 1, wherein the organic solvent is methanol, ethanol, acetone, ethyl acetate, chloroform.
5. The method of claim 1, wherein the powder lot obtained in step S3) is treated to remove conductive carbon and binder impurities contained therein before step S4); the processing method comprises the following steps: and mixing the powder with inorganic alkali, wherein the inorganic alkali is sodium hydroxide or potassium hydroxide, and then performing centrifugal separation and filtration.
6. The method according to claim 5, wherein the powder obtained by the centrifugal separation filtration is washed with deionized water and dried at room temperature; the concentration of the sodium hydroxide or the potassium hydroxide is 5 to 30 weight percent.
7. The method according to claim 1, wherein in step S5), the acidic solution is at least one selected from hydrochloric acid, nitric acid and sulfuric acid.
8. The method as claimed in claim 1, wherein the concentration of the acidic solution is 3 to 20wt% in step S5).
9. The method according to claim 1, wherein the mass-to-volume ratio of the powder to the acidic solution is 1:15 to 30.
10. The method according to claim 1, wherein the temperature of the recovery is set according to a temperature to which energy provided by the microwave irradiation is converted, and the temperature is 30 ℃ or more.
11. The method of claim 1, wherein the recovery time is 4 to 16 hours.
12. The method according to any one of claims 1 to 11, wherein the microwaves have a wavelength of between 1m and 1000nm and a frequency of between 300MHz and 300 GHz; the power of the irradiation is 200-800W.
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CN103915263A (en) * 2014-04-15 2014-07-09 中国科学院福建物质结构研究所 Method for recovering supercapacitor and electrode material of supercapacitor
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Publication number Priority date Publication date Assignee Title
JP2009224391A (en) * 2008-03-13 2009-10-01 Japan Gore Tex Inc Positive electrode material for lithium ion capacitor, and lithium ion capacitor
CN101948110A (en) * 2010-10-12 2011-01-19 昆明理工大学 Method for preparing activated carbons by using plastics of recycled waste circuit boards as raw material
CN103915263A (en) * 2014-04-15 2014-07-09 中国科学院福建物质结构研究所 Method for recovering supercapacitor and electrode material of supercapacitor
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