CN107117613B - A kind of preparation method of sulfur-bearing nitrogen active carbon - Google Patents
A kind of preparation method of sulfur-bearing nitrogen active carbon Download PDFInfo
- Publication number
- CN107117613B CN107117613B CN201710468009.9A CN201710468009A CN107117613B CN 107117613 B CN107117613 B CN 107117613B CN 201710468009 A CN201710468009 A CN 201710468009A CN 107117613 B CN107117613 B CN 107117613B
- Authority
- CN
- China
- Prior art keywords
- active carbon
- sulfur
- room temperature
- inert atmosphere
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of preparation method of sulfur-bearing nitrogen active carbon is by amine, aldehydes is added in reactor, pH value is adjusted between 8-9 with aqueous slkali, 50 DEG C -59 DEG C are warming up under stirring, the phenols for being dissolved in dehydrated alcohol is added in above-mentioned solution the 1-3h that flows back, is cooled to room temperature by constant temperature 10-30min, vacuum drying removes remaining ethyl alcohol, then solidifies；In an inert atmosphere, it carbonizes, is 1:1-6 according to charing sample and alkali mass ratio; it is risen at 600-850 DEG C with the heating rate of 3-5 DEG C/min by room temperature under inert atmosphere protection and activates 1-3h; after cooled to room temperature, deionized water is washed till neutrality, obtains sulfur-bearing nitrogen active carbon after dry.The present invention has the advantages that contain nitrogen, sulphur in high-specific surface area, surface and body phase simultaneously.
Description
Technical field
The invention belongs to a kind of methods for preparing sulfur and nitrogen co-doped active carbon.
Background technique
Active carbon is as a kind of carbonaceous porous material, because it is with biggish specific surface area, flourishing pore structure, surface
The advantages that chemical property is adjustable and be widely used in the multiple fields such as absorption, catalysis, environmental protection.Hetero atom in active carbon, as oxygen,
Its absorption and chemical property to gas can be improved in sulphur, nitrogen etc..After hetero atom in adjustment active carbon can use
The method of reason, Mangun et al. is by obtaining the activated carbon fibre that surface is rich in alkaline amido with ammonia activation, the absorption to CO2
Performance improves (Carbon, 2001,39,1809-1820).Another method is using containing heteroatomic presoma, and gold is small
Juans etc. (patent CN102360959A) make raw material using the Lauxite rich in nitrogen, after raw material is carbonized under an inert atmosphere
It carbonized after being blended with potassium hydroxide, activate the active carbon that preparation is rich in nitrogen.(patent CN105289686A) such as Liu Yongjun: will
Powdered carbon, binder and hetero atom predecessor, which are put into kneader, to be mediated to uniform, extrusion forming, drying is sufficiently mixed, and high temperature is living
The active carbon of sulfur-bearing, nitrogen has been made after change.These above-mentioned methods can all influence the pore structure of active carbon, or only in activated carbon surface
Increase hetero atom, and without containing hetero atom used when post-processing in activated carbon bodies phase, hetero atom is easy to run off.
Benzoxazine compares traditional phenolic resin or ammonia as a kind of novel thermosetting property, high performance resinamines
Base resin, has many advantages, such as.It is the nitrogenous active carbon of precursor preparation it has been reported that patent using benzoxazine resin
CN102225996B, using phenol, aldehyde, amine as raw material, water is to be contained after solvent is prepared for benzoxazine resin, then carbonization-activation
The activated carbon microballon of nitrogen.Patent CN105273188A provides a kind of self-catalysis preparation side for being copolymerized benzoxazine resin based carbon balls
Method, this method obtain corresponding charcoal ball after being calcined obtained copolymerization benzoxazine resin high score bulbec.Patent
CN104925781B, CN104310396B are prepared for nitrogenous multistage mesoporous activated carbon with F127 etc. for soft template and are used to adsorb
CO2Or as electrode material.Nitrogen is contained only in the Carbon Materials of the above method preparation.And element sulphur can also improve in active carbon
The physicochemical properties (Carbon, 2014,68,1-32) of active carbon.Simultaneously containing nitrogen, sulphur active carbon preparation method through retrieving
It has not been reported.
Summary of the invention
The purpose of the present invention is to provide in a kind of high-specific surface area, surface and body phase simultaneously containing nitrogen, sulphur active carbon
Preparation method.
Preparation method of the invention includes the following steps:
(1) by amine, aldehydes is added in reactor, adjusts pH with the potassium hydroxide or sodium hydroxide solution of 0.1M-0.9M
Value is warming up to 50 DEG C -59 DEG C, constant temperature 10-30min between 8-9 under stirring, above-mentioned solution is added in the phenols for being dissolved in ethyl alcohol
In, stir the lower 1-3h that flows back, be cooled to room temperature, vacuum drying removes remaining ethyl alcohol at 30 DEG C -60 DEG C, then 110 DEG C -
Solidify 3-6h at 240 DEG C；
(2) in an inert atmosphere, sample rises to 600 DEG C -800 with the heating rate of 1-5 DEG C/min after step (1) being solidified
At DEG C, constant temperature carbonizes 1-3h, and Temperature fall is 1:1-6 according to charing sample and potassium hydroxide or sodium hydroxide mass ratio, by charcoal
Change sample to be risen to the heating rate of 3-5 DEG C/min by room temperature under inert atmosphere protection with potassium hydroxide or sodium hydrate solid
Activate 1-3h at 600-850 DEG C, after cooled to room temperature, deionized water is washed till neutrality, it is dry after sulfur-bearing nitrogen active carbon.
Amine used is thiocarbamide, urea as described above；Aldehydes is formaldehyde, paraformaldehyde；Phenols is bisphenol S, thiobis benzene
Phenol, benzenethiol etc. are containing the mixing of one or more of thiophenols.
Phenols as described above: amine: aldehydes: dehydrated alcohol molar ratio is 1:1-2:1-6:10-20.
Advantages of the present invention is as follows:
1, since this patent uses sulfur-bearing, the compound of nitrogen quantity is polymerize, therefore also contain sulphur, nitrogen in gained polymers；
Sulphur nitrogen is all contained on charing, the body phase of activity following activation charcoal and surface, and between 12.7 wt%-25.9wt%, sulfur content exists nitrogen content
Between 0.6wt%-1.1wt%.
2, the method that this patent uses chemical activation, the specific surface area of products obtained therefrom is in 1685-2439 m2Between/g,
It is apparently higher than the performance of conventional physical activation products obtained therefrom.
Specific embodiment
Embodiment 1
Thiocarbamide and formaldehyde are added in reactor according to molar ratio for 1:4, adjust pH value with the potassium hydroxide solution of 0.1M
It is 8, stirring is warming up to 50 DEG C, constant temperature 10min.Bisphenol S (being 1:1 with thiocarbamide molar ratio) is dissolved in the anhydrous second of 10 times of moles
It in alcohol, is then added in above-mentioned reactor, stirs the lower 1h that flows back.It is cooled to room temperature, is dried in vacuo at 30 DEG C, remove ethyl alcohol,
Then solidify 3h at 250 DEG C.In an inert atmosphere, sample after solidification is risen at 600 DEG C with the heating rate of 5 DEG C/min,
Constant temperature carbonizes 1h, Temperature fall.It is 1:2 according to charing sample and potassium hydroxide quality ratio, charing sample is consolidated with potassium hydroxide
Body is risen at 700 DEG C by room temperature with the heating rate of 3 DEG C/min under inert atmosphere protection and activates 1h, cooled to room temperature
Afterwards, deionized water is washed till neutrality, obtains sulfur-bearing nitrogen active carbon after dry.Specific surface area 2038m2/ g, N content 18.7wt%, S content
0.9 wt%。
Embodiment 2
Thiocarbamide and formaldehyde are added in reactor according to molar ratio for 1:1, adjust pH value with the potassium hydroxide solution of 0.9M
Between 9, stirring is warming up to 59 DEG C, constant temperature 30min.Thio biphenol (being 1:2 with thiocarbamide molar ratio) is dissolved in 20 times moles
It in the dehydrated alcohol of amount, is then added in above-mentioned reactor, stirs the lower 3h that flows back.It is cooled to room temperature, is dried in vacuo at 60 DEG C,
Ethyl alcohol is removed, then solidifies 6h at 110 DEG C.In an inert atmosphere, sample after solidification is risen to the heating rate of 1 DEG C/min
At 800 DEG C, constant temperature carbonizes 3h, Temperature fall.It is 1:6 according to charing sample and potassium hydroxide quality ratio, by charing sample and hydrogen
Potassium oxide solid is risen at 850 DEG C by room temperature with the heating rate of 5 DEG C/min under inert atmosphere protection and activates 3h, natural cooling
To room temperature, a large amount of deionized waters are washed till neutrality, and the active carbon of sulfur-bearing nitrogen is obtained after dry.Specific surface area 2439m2/ g, N content
12.7wt%, S content 0.6wt%.
Embodiment 3
Urea and formaldehyde are added in reactor according to molar ratio for 1:6, adjust pH value with the potassium hydroxide solution of 0.5M
It is 8, stirring is warming up to 55 DEG C, constant temperature 15min.Benzenethiol (being 1:1 with urea mol ratio) is dissolved in the anhydrous of 15 times of moles
It in ethyl alcohol, is then added in above-mentioned reactor, stirs the lower 1h that flows back.It is cooled to room temperature, is dried in vacuo at 50 DEG C, remove second
Then alcohol solidifies 3h at 200 DEG C.In an inert atmosphere, sample after solidification is risen to 700 DEG C with the heating rate of 3 DEG C/min
Under, constant temperature carbonizes 2h, Temperature fall.It is 1:3 according to charing sample and sodium hydroxide mass ratio, by charing sample and sodium hydroxide
Solid is risen at 600 DEG C by room temperature with the heating rate of 5 DEG C/min under inert atmosphere protection and activates 3h, cooled to room temperature
Afterwards, a large amount of deionized waters are washed till neutrality, and the active carbon of sulfur-bearing nitrogen is obtained after dry.Specific surface area 1685m2/ g, N content 20.9wt%,
S content 0.94wt%.
Embodiment 4
Sulphur urine and formaldehyde are added in reactor according to molar ratio for 1:4, adjust pH value with the sodium hydroxide solution of 0.5M
It is 9, stirring is warming up to 55 DEG C, constant temperature 15min.Thio biphenol (being 1:1 with thiocarbamide molar ratio) is dissolved in 20 times of moles
It in dehydrated alcohol, is then added in above-mentioned reactor, stirs the lower 2h that flows back.It is cooled to room temperature, is dried in vacuo at 40 DEG C, removed
Then ethyl alcohol solidifies 3h at 180 DEG C.In an inert atmosphere, sample after solidification is risen to 700 with the heating rate of 3 DEG C/min
At DEG C, constant temperature carbonizes 1h, Temperature fall.It is 1:1 according to charing sample and potassium hydroxide quality ratio, by charing sample and hydroxide
Potassium solid is risen at 700 DEG C by room temperature with the heating rate of 3 DEG C/min under inert atmosphere protection and activates 3h, naturally cools to room
Wen Hou, a large amount of deionized waters are washed till neutrality, the active carbon of sulfur-bearing nitrogen are obtained after dry.Specific surface area 1751m2/ g, N content
22.9wt%, S content 0.83wt%.
Embodiment 5
Sulphur urine and paraformaldehyde are added in reactor according to molar ratio for 1:3, adjusted with the potassium hydroxide solution of 0.5M
PH value is 9, and stirring is warming up to 59 DEG C, constant temperature 15min.Thio biphenol (being 1:2 with thiocarbamide molar ratio) is dissolved in 20 times moles
It in the dehydrated alcohol of amount, is then added in above-mentioned reactor, stirs the lower 3h that flows back.It is cooled to room temperature, is dried in vacuo at 50 DEG C,
Ethyl alcohol is removed, then solidifies 6h at 250 DEG C.In an inert atmosphere, sample after solidification is risen to the heating rate of 3 DEG C/min
At 600 DEG C, constant temperature carbonizes 1h, Temperature fall.It is 1:2 according to charing sample and potassium hydroxide quality ratio, by charing sample and hydrogen
Potassium oxide solid is risen at 700 DEG C by room temperature with the heating rate of 3 DEG C/min under inert atmosphere protection and activates 1h, natural cooling
To room temperature, a large amount of deionized waters are washed till neutrality, and the active carbon of sulfur-bearing nitrogen is obtained after dry.Specific surface area 2372m2/ g, N content
25.9wt%, S content 1.1wt%.
Embodiment 6
Sulphur urine and formaldehyde are added in reactor according to molar ratio for 1:4, adjust pH value with the potassium hydroxide solution of 0.8M
It is 8.7, stirring is warming up to 59 DEG C, constant temperature 30min.Bisphenol S (being 1:1 with thiocarbamide molar ratio) is dissolved in the anhydrous of 17 times of moles
It in ethyl alcohol, is then added in above-mentioned reactor, stirs the lower 2h that flows back.It is cooled to room temperature, is dried in vacuo at 40 DEG C, remove second
Then alcohol solidifies 6h at 230 DEG C.In an inert atmosphere, sample after solidification is risen to 700 DEG C with the heating rate of 2 DEG C/min
Under, constant temperature carbonizes 2h, Temperature fall.It is 1:2 according to charing sample and potassium hydroxide quality ratio, by charing sample and potassium hydroxide
Solid is risen at 800 DEG C by room temperature with the heating rate of 3 DEG C/min under inert atmosphere protection and activates 1h, cooled to room temperature
Afterwards, a large amount of deionized waters are washed till neutrality, and the active carbon of sulfur-bearing nitrogen is obtained after dry.Specific surface area 2006m2/ g, N content 20.7wt%,
S content 0.76wt%.
Embodiment 7
Urea and paraformaldehyde are added in reactor according to molar ratio for 1:3, adjusted with the potassium hydroxide solution of 0.5M
PH value is 8.3, and stirring is warming up to 50 DEG C, constant temperature 10min.Bisphenol S (being 1:2 with urea mol ratio) is dissolved in 13 times of moles
It in dehydrated alcohol, is then added in above-mentioned reactor, stirs the lower 2h that flows back.It is cooled to room temperature, is dried in vacuo at 40 DEG C, removed
Then ethyl alcohol solidifies 5h at 210 DEG C.In an inert atmosphere, sample after solidification is risen to 750 with the heating rate of 3 DEG C/min
At DEG C, constant temperature carbonizes 1h, Temperature fall.It is 1:3 according to charing sample and sodium hydroxide mass ratio, by charing sample and hydroxide
Sodium solid is risen at 700 DEG C by room temperature with the heating rate of 4 DEG C/min under inert atmosphere protection and activates 2h, naturally cools to room
Wen Hou, a large amount of deionized waters are washed till neutrality, the active carbon of sulfur-bearing nitrogen are obtained after dry.Specific surface area 1978m2/ g, N content
18.6wt%, S content 0.85wt%.
Embodiment 8
Sulphur urine and paraformaldehyde are added in reactor according to molar ratio for 1:5, adjusted with the potassium hydroxide solution of 0.5M
PH value is 8.5, and stirring is warming up to 40 DEG C, constant temperature 30min.Benzenethiol (being 1:1 with thiocarbamide molar ratio) is dissolved in 17 times of moles
Dehydrated alcohol in, be then added in above-mentioned reactor, stir the lower 3h that flows back.It is cooled to room temperature, is dried in vacuo, removes at 58 DEG C
Ethyl alcohol is removed, then solidifies 6h at 200 DEG C.In an inert atmosphere, sample after solidification is risen to the heating rate of 3 DEG C/min
At 700 DEG C, constant temperature carbonizes 3h, Temperature fall.It is 1:5 according to charing sample and sodium hydroxide mass ratio, by charing sample and hydrogen
Sodium oxide molybdena solid is risen at 750 DEG C by room temperature with the heating rate of 4 DEG C/min under inert atmosphere protection and activates 2h, natural cooling
To room temperature, a large amount of deionized waters are washed till neutrality, and the active carbon of sulfur-bearing nitrogen is obtained after dry.Specific surface area 2012m2/ g, N content
20.4wt%, S content 1.1wt%.
Embodiment described above is merely a preferred embodiment of the present invention, and the simultaneously exhaustion of the feasible implementation of non-present invention.It is right
For persons skilled in the art, any aobvious to made by it under the premise of without departing substantially from the principle of the invention and spirit and
The change being clear to should be all contemplated as falling within claims of the invention.
Claims (3)
1. a kind of preparation method of sulfur-bearing nitrogen active carbon, it is characterised in that include the following steps:
(1) by amine, aldehydes is added in reactor, is adjusted pH value with the potassium hydroxide or sodium hydroxide solution of 0.1M-0.9M and is existed
Between 8-9, it is warming up to 50 DEG C -59 DEG C, constant temperature 10-30min under stirring, above-mentioned solution is added in the phenols for being dissolved in dehydrated alcohol
In, stir the lower 1-3h that flows back, be cooled to room temperature, vacuum drying removes remaining ethyl alcohol at 30 DEG C -60 DEG C, then 110 DEG C -
Solidify 3-6h at 240 DEG C；
The amine is thiocarbamide or urea；The phenols is one of bisphenol S or thio biphenol, benzenethiol or several；
(2) in an inert atmosphere, sample rises to 600 DEG C -800 DEG C with the heating rate of 1-5 DEG C/min after step (1) being solidified
Under, constant temperature carbonizes 1-3h, and Temperature fall is 1:1-6 according to charing sample and potassium hydroxide or sodium hydroxide mass ratio, will carbonize
Sample and potassium hydroxide or sodium hydroxide rise to 600- by room temperature with the heating rate of 3-5 DEG C/min under inert atmosphere protection
Activate 1-3h at 850 DEG C, after cooled to room temperature, deionized water is washed till neutrality, it is dry after sulfur-bearing nitrogen active carbon.
2. a kind of preparation method of sulfur-bearing nitrogen active carbon as described in claim 1, it is characterised in that the aldehydes be formaldehyde or
Paraformaldehyde.
3. a kind of preparation method of sulfur-bearing nitrogen active carbon as described in claim 1, it is characterised in that the phenols: amine: aldehyde
Class: dehydrated alcohol molar ratio is 1:1-2:1-6:10-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710468009.9A CN107117613B (en) | 2017-06-20 | 2017-06-20 | A kind of preparation method of sulfur-bearing nitrogen active carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710468009.9A CN107117613B (en) | 2017-06-20 | 2017-06-20 | A kind of preparation method of sulfur-bearing nitrogen active carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107117613A CN107117613A (en) | 2017-09-01 |
| CN107117613B true CN107117613B (en) | 2019-06-25 |
Family
ID=59718454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710468009.9A Active CN107117613B (en) | 2017-06-20 | 2017-06-20 | A kind of preparation method of sulfur-bearing nitrogen active carbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107117613B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109748279A (en) * | 2019-02-21 | 2019-05-14 | 南京大学 | One kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application |
| CN111554519A (en) * | 2020-05-13 | 2020-08-18 | 陈志林 | α -Bi2O3Carbon material-loaded supercapacitor electrode material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925781B (en) * | 2015-06-09 | 2016-09-21 | 中国科学院山西煤炭化学研究所 | One has high CO simultaneously2the preparation method of the nitrogen-enriched layer secondary aperture charcoal of quantity of the catch and high specific capacitance |
| CN105948045B (en) * | 2016-07-18 | 2018-04-03 | 湘潭大学 | A kind of preparation method and applications of N doping starch base activated carbon microballon material |
-
2017
- 2017-06-20 CN CN201710468009.9A patent/CN107117613B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107117613A (en) | 2017-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107519892B (en) | A kind of support type oxidative esterification catalyst and its preparation method and application | |
| CN107117613B (en) | A kind of preparation method of sulfur-bearing nitrogen active carbon | |
| RU2012118391A (en) | SUSTAINABLE CATALYST CARRIER BASED ON ALUMINUM OXIDE | |
| CN103787388B (en) | A kind of preparation method of alumina support | |
| CN107175340B (en) | A kind of preparation method of core-shell structure Cu@Ag nanoparticle | |
| WO2011103698A1 (en) | Hydro refining catalyst | |
| CN108371953B (en) | It is a kind of for the BCN catalyst of Knoevenagel condensation reaction and its preparation and application | |
| JP2013521218A (en) | Method for producing base activated carbon | |
| CN109110742A (en) | Utilize the mesoporous carbon and preparation method of manganese compound preparation | |
| CN104275185A (en) | Preparation method of copper-based hydrogenation catalyst without reduction activation | |
| CN111420702A (en) | High-activity water-resistant sulfur-resistant low-temperature SCR denitration catalyst and preparation method thereof | |
| CN105460918A (en) | Preparation method of hollow carbon sphere | |
| CN105664850B (en) | A kind of preparation method and applications of high performance carbon base carbon dioxide sorbing material | |
| CN101966470B (en) | Rare-earth desulfurization catalyst and preparation method thereof | |
| CN103059657A (en) | Low temperature energy saving powder coating | |
| Fan et al. | Effect of components upon the surface area of woodceramics | |
| CN102516322A (en) | Method for preparing levoglucosenone with magnetic solid phosphoric acid catalyst | |
| CN110240595A (en) | The preparation method and application of phentriazine class compound as polyvinyl chloride light stabilizer | |
| CN111545162A (en) | Sulfur dioxide adsorbent and preparation method thereof | |
| CN109384213A (en) | A kind of preparation method of phenol-urea-formaldehyde condensation copolymerization resin base N doping charcoal-aero gel | |
| CN101831042B (en) | Preparation method of thermoplastic phenolic resin with high solid content | |
| CN110066416B (en) | Preparation method of phenolic resin foam and carbon foam | |
| CN113457627A (en) | Polybenzoxazinyl derived carbon material for adsorbing carbonyl sulfide and preparation method and application thereof | |
| CN103508860B (en) | Method for preparing polyoxymethylene dimethylethers from methanol and formaldehyde | |
| CN115215337B (en) | Method for synthesizing phenolic resin and preparing carbon material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |