CN108128774A - A kind of preparation method of high-purity porous charcoal - Google Patents

A kind of preparation method of high-purity porous charcoal Download PDF

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Publication number
CN108128774A
CN108128774A CN201810171622.9A CN201810171622A CN108128774A CN 108128774 A CN108128774 A CN 108128774A CN 201810171622 A CN201810171622 A CN 201810171622A CN 108128774 A CN108128774 A CN 108128774A
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China
Prior art keywords
porous charcoal
resin
alkali metal
metal salt
water
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CN201810171622.9A
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Chinese (zh)
Inventor
杨瑞甫
余荣彬
张金亮
丁玉珍
杨裕生
徐乐乐
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Zhangjiagang Bowei New Energy Material Research Institute Co Ltd
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Zhangjiagang Bowei New Energy Material Research Institute Co Ltd
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Abstract

The invention discloses a kind of preparation methods of high-purity porous charcoal, and alkali metal salt soluble easily in water is mixed with water soluble high molecular material, carry out pre-reaction and obtain mixture;High molecular material is made of the one or more in resin, cellulose, cellulose derivative;Mixture is broken into the particle that grain size is 0.01 5mm again;And under an inert atmosphere by particle with the heating rate of 1 20 DEG C/min, 600 1000 DEG C are warming up to, and keep 0.5 8h, particle is carbonized and is activated, porous charcoal is made;Porous charcoal after cooling finally is impregnated with solution, dissolves remaining alkali metal salt, after repeatedly washing, dry porous charcoal.A kind of preparation method of high-purity porous charcoal of the present invention, the specific surface area of porous charcoal obtained are up to 1200 2100m2/g;Remaining alkali metal salt is used only water and can be completely dissolved, removed, and does not need to the processes such as pickling processes, and content of ashes is less than 0.5%, not the impurity such as iron content, chlorine, and product purity is high, is conducive to extend equipment life, reduces the pollution to environment.

Description

A kind of preparation method of high-purity porous charcoal
Technical field
The present invention relates to fine chemistry industry and new energy materials preparation field, more particularly to a kind of preparation of high-purity porous charcoal Method.
Background technology
Porous charcoal has the characteristics that hole enriches, large specific surface area, chemically and thermally stability is high, good conductivity, in gas Absorption, chromatographic isolation, catalyst carrier, electrode material etc. have a wide range of applications.
Different application fields is different to the requirement of the physicochemical property of porous charcoal, in fields such as biological medicine, electrochemical storages, In addition to pore structure is flourishing, also require porous charcoal that there is high degree of purity.Especially as ultracapacitor, battery electrode material Electrochemical applications, in order to avoid side reaction is by caused performance degradation, have strict demand to the content of metal impurities.
The traditional preparation method of porous carbon material mainly use biomass such as shell, timber, coal, petroleum coke, pitches or Mineral raw material carries out physics or chemical activation, and due to these raw materials, impurity itself is more, and the porous charcoal prepared is often miscellaneous Matter content is higher, and the purity of product, but complex technical process can be improved by techniques such as pickling, alkali cleanings, cost is made to increase Add.People had developed the method that porous charcoal is prepared using high molecular material as carbon matrix precursor in recent years, because raw metal impurity is few, changes It is controllable to learn the Nomenclature Composition and Structure of Complexes, the product haveing excellent performance can be prepared.
A kind of method is activated using KOH, NaOH, as Chinese patent CN1807235A disclose it is a kind of using novolac The phenolic resin particle of crushing is mixed and ground with curing agent, activator KOH by the method that resin prepares active carbon with high specific surface area Mill, then carbonizes under an inert atmosphere, follow-up by washing, pickling, is finally washed to neutrality, high-specific surface area is obtained after dry Carbon Materials.Alkali activation product specific surface area is high, but highly basic is also extremely serious to the corrosion of equipment and the destruction of environment.
Another method is using form technology, mainly using silicon substrates templates, such as Chinese patent such as molecular sieves CN102976305A discloses a kind of preparation method of the Mesoporous Carbon Materials in template regulation and control aperture, by polyethers F127, homemade Silicon oxide ball template and phenolic resin mixing, through charing, HF pickling, washing, dry obtained mesoporous carbon materials.Because remove silicon Basic mode plate needs HF to etch, and corrosivity is too strong, and people have developed the method that the insoluble inorganic salts such as MgO, CaCO3 do template again, but There is still a need for remove template procedure, complex process with hydrochloric acid etc. after charing.
Invention content
The object of the present invention is to provide a kind of preparation methods of high-purity porous charcoal, solve and use highly basic in the prior art As caused by activator the problem of the environmental pollution of equipment burn into, at the same solve and dissolved using acid solution, it is prepared by removing hard template The complex process problem of porous charcoal.
In order to achieve the above objectives, the technical solution adopted by the present invention is:
A kind of preparation method of high-purity porous charcoal, includes the following steps:
(1)Alkali metal salt soluble easily in water with water soluble high molecular material is mixed, pre-reaction is carried out and obtains mixture;It is described High molecular material is made of the one or more in resin, cellulose, cellulose derivative;
(2)The mixture is broken into the particle that grain size is 0.01-5mm;
(3)The particle is warming up to 600-1000 DEG C, and keep with the heating rate of 1-20 DEG C/min under an inert atmosphere 0.5-8h is carbonized and is activated to the particle, and porous charcoal is made;
(4)The porous charcoal after cooling is impregnated with solution, dissolves the remaining alkali metal salt, after repeatedly washing, is done The dry porous charcoal.
Preferably, the alkali metal salt is by sodium carbonate, sodium acetate, sodium citrate, sodium oxalate, sodium sulphate, sodium nitrate, carbonic acid One or more kinds of compositions in potassium, potassium acetate, potassium oxalate, potassium sulfate, potassium nitrate.
It is highly preferred that the solution includes distilled water, deionized water and does not contain and can react life with carbonate, sulfate radical Fresh water, low concentration brine, low concentration buck into the ion of sediment.
Preferably, the resin is by phenolic resin, Lauxite, epoxy resin, alkyd resin, amino resins, polyester tree One or more kinds of compositions in fat, acrylic resin, polyurethane resin, furane resins, melamine resin.
Preferably, in step(1)In, when the alkali metal salt is mixed with the high molecular material, while add in curing Agent is cured after pre-reaction.
It is highly preferred that the curing agent is by hexamethylenetetramine, propene carbonate, polyformaldehyde, urea, m-phenylene diamine (MPD), suitable One or more kinds of compositions in anhydride maleique, dicyandiamide, ammonium chloride, trimethyl phosphate, diethy-aceto oxalate.
It is highly preferred that the mass ratio of the high molecular material, the alkali metal salt, the curing agent is 1:0.1-20: 0- 0.5, wherein, not including endpoint 0.
It is highly preferred that cured temperature is 90-180 DEG C, the cured time is 0.5-24h.
Preferably, in step(1)In, the temperature of pre-reaction is 50-90 DEG C, and the time of pre-reaction is 0.5-24h.
Preferably, the high molecular material, the alkali metal salt mass ratio be 1:0.1-20.
Due to the utilization of above-mentioned technical proposal, the present invention has following advantages compared with prior art:The present invention is a kind of high The preparation method of purity porous charcoal, alkali metal salt is first dissolved in water in raw material mixed process, can realize molecule with water-soluble resin Grade dispersion, after resin solidification, dehydration, alkali metal salt forms nano crystals in mixture, and serves as hard mold at charing initial stage Plate acts on, and constructs a large amount of micropores;High temperature carbonization stage, alkali metal salt or its converted product play in-situ activation effect, continue Micropore and mesoporous are made, double action so that product hole is flourishing, and specific surface area is up to 1200-2100m2/g;Last remaining alkali Metal salt is used only water and can be completely dissolved, removed, and does not need to the processes such as pickling processes, and content of ashes is less than 0.5%, no The impurity such as iron content, chlorine, product purity is high, is suitable for use as the electrochemical energy storages key electrode material such as ultracapacitor, fuel cell. Simple for process inventive process avoids complex processes such as pickling, the alkali metal salt of use is far below often the corrosivity of equipment KOH, NaOH alkali activator are conducive to extend equipment life, can substantially reduce production cost, while also reduce to environment Adverse effect.
Specific embodiment
Technical scheme of the present invention is further elaborated with reference to specific embodiment.
Embodiment 1
Water soluble phenol resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in 4.5g hexamethylenetetramines With 135g sodium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.It will stir evenly Mixture be transferred in beaker, be placed in 150 DEG C of baking oven openings and place 12h.Then 0.2-1mm is crushed to, in nitrogen atmosphere Under carbonized, carbonization heating rate be 8 DEG C/min, charing final temperature be 900 DEG C, final temperature heat preservation 1h, cooled to room temperature.It takes Go out carbide, washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is dried in 120 DEG C of vacuum drying ovens 6h, the specific surface area of porous charcoal obtained is 1357m2/ g, total pore volume 0.8cm3g-1, content of ashes is 0.3% (mass ratio).
Embodiment 2
Water soluble phenol resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in six methines four of 4.5g Amine and 135g potassium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.It will stir equal Even mixture is transferred in beaker, is placed in 150 DEG C of baking oven sealings and is placed 12h.Then 0.2-1mm is crushed to, in tubular type liter It is carbonized in warm stove, carbonization heating rate is 8 DEG C/min, and charing final temperature is 900 DEG C, and final temperature heat preservation 1h naturally cools to room Temperature, whole nitrogen protection.Carbide is taken out, is washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is 120 6h is dried in DEG C vacuum drying oven, the specific surface area of porous charcoal obtained is 2054m2/ g, total pore volume 1.1cm3g-1, content of ashes For 0.4% (mass ratio).
Embodiment 3
Water soluble phenol resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in six methines four of 4.5g Amine and 135g potassium acetates, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.It will stir evenly Mixture be transferred in beaker, be placed in 150 DEG C of baking ovens and place 12h.Then 0.2-1mm is crushed to, in tubular type heating furnace It is carbonized, carbonization heating rate is 8 DEG C/min, and charing final temperature is 900 DEG C, final temperature heat preservation 1h, and cooled to room temperature is whole Nitrogen is protected.Carbide is taken out, is washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is in 120 DEG C of vacuum 6h is dried in baking oven, the specific surface area of porous charcoal obtained is 1912m2/ g, total pore volume 1.0cm3g-1, content of ashes is 0.2% (mass ratio).
Embodiment 4
Water soluble phenol resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in six methines four of 4.5g Amine and 135g sodium oxalates, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.It will stir evenly Mixture be transferred in beaker, be placed in 150 DEG C of baking ovens and place 12h.Then 0.2-1mm is crushed to, in tubular type heating furnace It is carbonized, carbonization heating rate is 8 DEG C/min, and charing final temperature is 900 DEG C, final temperature heat preservation 1h, and cooled to room temperature is whole Nitrogen is protected.Carbide is taken out, is washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is in 120 DEG C of vacuum 6h is dried in baking oven, the specific surface area of porous charcoal obtained is 1571m2/ g, total pore volume 0.76cm3g-1, content of ashes is 0.2% (mass ratio).
Embodiment 5
Water soluble phenol resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in six methines four of 4.5g Amine and 135g sodium sulphate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.It will stir evenly Mixture be transferred in beaker, be placed in 150 DEG C of baking ovens and place 12h.Then 0.2-1mm is crushed to, under tubular type heating furnace It is carbonized, carbonization heating rate is 8 DEG C/min, and charing final temperature is 900 DEG C, final temperature heat preservation 1h, and cooled to room temperature is whole Nitrogen is protected.Carbide is taken out, is washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is in 120 DEG C of vacuum 6h is dried in baking oven, the specific surface area of porous charcoal obtained is 1414m2/ g, total pore volume 0.75cm3g-1, content of ashes is 0.3% (mass ratio).
Embodiment 6
Water-soluble urea-formaldehyde resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in 4.5g hexamethylenetetramines With 135g sodium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.By what is stirred evenly Mixture is transferred in beaker, is placed in 150 DEG C of baking ovens and is placed 12h.Then 0.5mm is crushed to, carries out charcoal in a nitrogen atmosphere Change, carbonization heating rate is 8 DEG C/min, and charing final temperature is 900 DEG C, final temperature heat preservation 1h, cooled to room temperature, and whole nitrogen is protected Shield.Carbide is taken out, is washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is in 120 DEG C of vacuum drying ovens 6h is dried, the specific surface area of porous charcoal obtained is 1226m2/ g, total pore volume 0.7cm3g-1, content of ashes is 0.3% (quality Than).
Embodiment 7
Water-soluble epoxy resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in 4.5g hexamethylenetetramines With 135g sodium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.By what is stirred evenly Mixture is transferred in beaker, is placed in 150 DEG C of baking ovens and is placed 12h.Then 0.5mm is crushed to, carries out charcoal in a nitrogen atmosphere Change, carbonization heating rate is 8 DEG C/min, and charing final temperature is 900 DEG C, final temperature heat preservation 1h, cooled to room temperature, and whole nitrogen is protected Shield.Carbide is taken out, is washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is in 120 DEG C of vacuum drying ovens 6h is dried, the specific surface area of porous charcoal obtained is 1434m2/ g, total pore volume 0.75cm3g-1, content of ashes is 0.4% (quality Than).
Embodiment 8
Water soluble amino resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in 4.5g hexamethylenetetramines With 135g sodium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.By what is stirred evenly Mixture is transferred in beaker, is placed in 150 DEG C of baking ovens and is placed 12h.Then 0.5mm is crushed to, carries out charcoal in a nitrogen atmosphere Change, carbonization heating rate is 8 DEG C/min, and charing final temperature is 900 DEG C, final temperature heat preservation 1h, cooled to room temperature, and whole nitrogen is protected Shield.Carbide is taken out, is washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is in 120 DEG C of vacuum drying ovens 6h is dried, the specific surface area of porous charcoal obtained is 1324m2/ g, total pore volume 0.7cm3g-1, content of ashes is 0.3% (quality Than).
Embodiment 9
Water-soluble polyester resin 100g is weighed, pours into three-necked flask, is placed in 60 DEG C of water-baths, adds in 4.5g hexamethylenetetramines With 135g sodium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.By what is stirred evenly Mixture is transferred in beaker, is placed in 150 DEG C of baking ovens and is placed 12h.Then 0.5mm is crushed to, carries out charcoal in a nitrogen atmosphere Change, carbonization heating rate is 8 DEG C/min, and charing final temperature is 900 DEG C, final temperature heat preservation 1h, cooled to room temperature, and whole nitrogen is protected Shield.Carbide is taken out, is washed, filtered to neutrality repeatedly with 100 DEG C of deionized waters.Products therefrom is in 120 DEG C of vacuum drying ovens 6h is dried, the specific surface area of porous charcoal obtained is 1451m2/ g, total pore volume 0.75cm3g-1, content of ashes is 0.3% (quality Than).
Embodiment 10
Weigh water soluble phenol resin 100g, pour into three-necked flask, heating water bath to 60 DEG C, add in 4.5g hexamethylenetetramines and 135g sodium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.It is mixed by what is stirred evenly It closes object to be transferred in beaker, is placed in 150 DEG C of baking oven openings and places 12h.Then 0.5mm is crushed to, is carried out in a nitrogen atmosphere Charing, carbonization heating rate are 8 DEG C/min, and charing final temperature is 700 DEG C, final temperature heat preservation 1h, cooled to room temperature.Take out charing Object with 100 DEG C of deionized waters is washed, filtered to neutrality repeatedly.Products therefrom dries 6h in 120 DEG C of vacuum drying ovens, is made Porous charcoal specific surface area be 1810m2/ g, total pore volume 1.2cm3g-1, content of ashes is 0.3% (mass ratio).
Embodiment 11
Weigh water soluble phenol resin 100g, pour into three-necked flask, heating water bath to 60 DEG C, add in 4.5g hexamethylenetetramines and 135g sodium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.It is mixed by what is stirred evenly It closes object to be transferred in beaker, is placed in 150 DEG C of baking oven openings and places 12h.Then 0.5mm is crushed to, is carried out in a nitrogen atmosphere Charing, carbonization heating rate are 8 DEG C/min, and charing final temperature is 800 DEG C, final temperature heat preservation 1h, cooled to room temperature.Take out charing Object with 100 DEG C of deionized waters is washed, filtered to neutrality repeatedly.Products therefrom dries 6h in 120 DEG C of vacuum drying ovens, is made Porous charcoal specific surface area be 1530m2/ g, total pore volume 1.1cm3g-1, content of ashes is 0.3% (mass ratio).
Embodiment 12
Weigh water soluble phenol resin 100g, pour into three-necked flask, heating water bath to 60 DEG C, add in 4.5g hexamethylenetetramines and 135g sodium carbonate, mechanical agitation 30min.Then raising bath temperature continues heating stirring 1h to 85 DEG C.It is mixed by what is stirred evenly It closes object to be transferred in beaker, is placed in 150 DEG C of baking oven openings and places 12h.Then 0.5mm is crushed to, is carried out in a nitrogen atmosphere Charing, carbonization heating rate are 8 DEG C/min, and charing final temperature is 1000 DEG C, final temperature heat preservation 1h, cooled to room temperature.Take out charcoal Compound with 100 DEG C of deionized waters is washed, filtered to neutrality repeatedly.Products therefrom dries 6h in 120 DEG C of vacuum drying ovens, system The specific surface area of the porous charcoal obtained is 1210m2/ g, total pore volume 0.7cm3g-1, content of ashes is 0.3% (mass ratio).
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and be implemented, and it is not intended to limit the scope of the present invention, all according to the present invention The equivalent change or modification that Spirit Essence is made should all cover within the scope of the present invention.

Claims (10)

1. a kind of preparation method of high-purity porous charcoal, it is characterised in that:Include the following steps:
(1)Alkali metal salt soluble easily in water with water soluble high molecular material is mixed, pre-reaction is carried out and obtains mixture;It is described High molecular material is made of the one or more in resin, cellulose, cellulose derivative;
(2)The mixture is broken into the particle that grain size is 0.01-5mm;
(3)The particle is warming up to 600-1000 DEG C, and keep with the heating rate of 1-20 DEG C/min under an inert atmosphere 0.5-8h is carbonized and is activated to the particle, and porous charcoal is made;
(4)The porous charcoal after cooling is impregnated with solution, dissolves the remaining alkali metal salt, after repeatedly washing, is done The dry porous charcoal.
2. a kind of preparation method of high-purity porous charcoal according to claim 1, it is characterised in that:The alkali metal salt by Sodium carbonate, sodium acetate, sodium citrate, sodium oxalate, sodium sulphate, sodium nitrate, potassium carbonate, potassium acetate, potassium oxalate, potassium sulfate, nitric acid One or more kinds of compositions in potassium.
3. a kind of preparation method of high-purity porous charcoal according to claim 2, it is characterised in that:The solution includes steaming Distilled water, deionized water and the fresh water, the low concentration of salt that do not contain the ion that generation sediment can be reacted with carbonate, sulfate radical Water, low concentration buck.
4. a kind of preparation method of high-purity porous charcoal according to claim 1, it is characterised in that:The resin is by phenolic aldehyde Resin, Lauxite, epoxy resin, alkyd resin, amino resins, polyester resin, acrylic resin, polyurethane resin, furans One or more kinds of compositions in resin, melamine resin.
5. a kind of preparation method of high-purity porous charcoal according to claim 1, it is characterised in that:In step(1)In, it will When the alkali metal salt is mixed with the high molecular material, while curing agent is added in, cured after pre-reaction.
6. a kind of preparation method of high-purity porous charcoal according to claim 5, it is characterised in that:The curing agent is by six Methine tetramine, propene carbonate, polyformaldehyde, urea, m-phenylene diamine (MPD), maleic anhydride, dicyandiamide, ammonium chloride, tricresyl phosphate One or more kinds of compositions in methyl esters, diethy-aceto oxalate.
7. a kind of preparation method of high-purity porous charcoal according to claim 5, it is characterised in that:The macromolecule material Material, the alkali metal salt, the curing agent mass ratio be 1:0.1-20:0-0.5, wherein, not including endpoint 0.
8. a kind of preparation method of high-purity porous charcoal according to claim 5, it is characterised in that:Cured temperature is 90-180 DEG C, the cured time is 0.5-24h.
9. a kind of preparation method of high-purity porous charcoal according to claim 1, it is characterised in that:In step(1)In, in advance The temperature of reaction is 50-90 DEG C, and the time of pre-reaction is 0.5-24h.
10. a kind of preparation method of high-purity porous charcoal according to claim 1, it is characterised in that:The macromolecule material Expect, the mass ratio of the alkali metal salt is 1:0.1-20.
CN201810171622.9A 2018-03-01 2018-03-01 A kind of preparation method of high-purity porous charcoal Pending CN108128774A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108996502A (en) * 2018-08-27 2018-12-14 天津市职业大学 The method that 4-Hydroxyphenyl hydantoin production waste liquor prepares high performance active carbon
CN110451477A (en) * 2019-08-06 2019-11-15 大连理工大学 A kind of one-step method prepares the method and its application of phthalonitrile base porous carbon materials
CN110723733A (en) * 2018-07-16 2020-01-24 深圳市环球绿地新材料有限公司 Super-capacity carbon and preparation method and application thereof
CN110734060A (en) * 2018-07-19 2020-01-31 深圳市环球绿地新材料有限公司 Preparation method of super-capacity carbon

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Publication number Priority date Publication date Assignee Title
CN104709906A (en) * 2013-12-17 2015-06-17 中国科学院过程工程研究所 Preparation method of three dimensional graded porous activated carbon material
CN106587047A (en) * 2016-12-12 2017-04-26 张家港智电芳华蓄电研究所有限公司 Preparation method for nanoporous carbon

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104709906A (en) * 2013-12-17 2015-06-17 中国科学院过程工程研究所 Preparation method of three dimensional graded porous activated carbon material
CN106587047A (en) * 2016-12-12 2017-04-26 张家港智电芳华蓄电研究所有限公司 Preparation method for nanoporous carbon

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110723733A (en) * 2018-07-16 2020-01-24 深圳市环球绿地新材料有限公司 Super-capacity carbon and preparation method and application thereof
CN110734060A (en) * 2018-07-19 2020-01-31 深圳市环球绿地新材料有限公司 Preparation method of super-capacity carbon
CN110734060B (en) * 2018-07-19 2021-08-17 深圳市环球绿地新材料有限公司 Preparation method of super-capacity carbon
CN108996502A (en) * 2018-08-27 2018-12-14 天津市职业大学 The method that 4-Hydroxyphenyl hydantoin production waste liquor prepares high performance active carbon
CN110451477A (en) * 2019-08-06 2019-11-15 大连理工大学 A kind of one-step method prepares the method and its application of phthalonitrile base porous carbon materials

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