CN103936004A - Preparation method of resin-based spherical activated carbon with controllable pore structure - Google Patents
Preparation method of resin-based spherical activated carbon with controllable pore structure Download PDFInfo
- Publication number
- CN103936004A CN103936004A CN201410139231.0A CN201410139231A CN103936004A CN 103936004 A CN103936004 A CN 103936004A CN 201410139231 A CN201410139231 A CN 201410139231A CN 103936004 A CN103936004 A CN 103936004A
- Authority
- CN
- China
- Prior art keywords
- preparation
- active carbon
- spheric active
- resin
- room temperature
- 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.)
- Granted
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to a preparation method of resin-based spherical activated carbon with a controllable pore structure. The preparation method comprises the following steps: adding a phenol and an aldehyde into water according to the molar ratio of 1: (2-6), adding a catalyst accounting for 0.7-1% of the molar amount of the phenol into a solution, heating and increasing the temperature to 85-90 DEG C under stirring conditions, then adding a dispersant accounting for 10%-30% of the molar amount of the phenol, continuously stirring for 20-60min, then adding a curing agent accounting for 1%-3% of the molar amount of the phenol and a pore-forming agent accounting for 0-5% of the molar amount of the phenol, continuously stirring for 2-5h, cooling to room temperature, and filtering to obtain resin spheres; and carbonizing the prepared resin spheres under the protection of nitrogen, further activating, and reducing the temperature to room temperature to obtain the phenolic resin-based spherical activated carbon. The preparation method provided by the invention has the advantages of controllable aperture, mild operation conditions and low cost.
Description
Technical field
The invention belongs to a kind of method of preparing the controlled alkyd resin based spheric active carbon of pore structure.
Background technology
Spheric active carbon has the advantages such as good sphericity, adsorptive capacity is large, tamped density is even, resistance is little, has important effect at aspects such as catalysis, chemical separating, environmental protection, medical treatment.The raw material of preparing at present spheric active carbon comprises pitch, resol, polystyrene spheres etc.Because the raw material of resol is cheap and easy to get, and synthetic convenient, carbonization yield is high, and impure amount is low and have good physical strength and resistance toheat, and becomes the main precursor of preparing spheric active carbon.
Yang Junbing (patent No. CN98115717.3) etc. are by after resol, solidifying agent, solvent, removal of solvent under reduced pressure, carry out again fragmentation, sieve the particle that obtains predetermined particle size, by this particle and the aqueous solution that adds tensio-active agent, utilize emulsion process to prepare resin base bead, the resin base bead obtaining carries out obtaining alkyd resin based spheric active carbon, this method process complexity, poor reproducibility after charing, activation again.Wang Furong (patent No. CN200410012346.X) is taking water and alcohol mixture as solvent, polyvinyl alcohol is tensio-active agent, heating resol obtains resin beads, but the method is suitable for preparing micron order bead, and while producing bead more than 0.3mm, sphere diameter distributes and broadens.Li Kaixi (patent No. 101157451B) etc. adds pre-treatment material in the alcoholic solution of resol, then adds tensio-active agent, and mixture heated and stirred in autoclave arrives 110-140 DEG C.These methods all can not well regulate and control the aperture of spheric active carbon above, and in autoclave, react condition harshness.
Summary of the invention
The object of the present invention is to provide the alkyd resin based spheric active carbon preparation method that a kind of aperture is controlled, operational condition is gentle, with low cost.
The invention process process is as follows:
Be 1:(2-6 by phenols and aldehydes according to mol ratio) be added to the water, the catalyzer of phenols molar weight 0.7%-1% is added in above-mentioned solution, under the condition stirring, heat to 85-90 DEG C, then add the dispersion agent of phenols molar weight 10%-30%, continue to stir after 20-60 minute and add the solidifying agent of phenols molar weight 1%-3% and the pore-forming material of phenols molar weight 0-5%, continue to stir 2-5 hour, cool to room temperature, filters and obtains resin balls; By the resin balls of preparation, under nitrogen protection, be warming up to 700-1000 DEG C of charing by room temperature, and then pass into carbonic acid gas or water vapour activates, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon.
Phenols used described above be between ethylphenol, a tert.-butyl phenol, 1-naphthols, 1, one or more mixing in 5-dihydroxy naphthlene; Aldehydes is formaldehyde, paraformaldehyde; Catalyzer is triethylamine, ammoniacal liquor, sodium hydroxide, hydrated barta; Dispersion agent is polyvinyl alcohol, sodium laurylsulfonate, gum arabic; Solidifying agent is hexamethyl tetramine, trimeric cyanamide, aniline; Pore-forming material is polyoxyethylene glycol, ethylene glycol.
Carbonization condition as above is: temperature rise rate is 1-5 DEG C/min, and carbonization temperature is 700-1000 DEG C, and carbonization time is 0-1h.
Activation condition as above is: activation temperature is 700-1000 DEG C, and soak time is 1-3h.
Advantage of the present invention
1, from the aperture of molecule roofing control spheric active carbon.
2, with low cost, prepare phenolic resin balls with more basic raw material.
3, operational condition gentleness, balling-up reaction is carried out under normal pressure.
Embodiment
Embodiment 1
Between inciting somebody to action, ethylphenol and formaldehyde are that 1:4 is added to the water according to mol ratio, a triethylamine for ethylphenol molar weight 0.75% is added in above-mentioned solution, under the condition stirring, heat to 85 DEG C, then the polyvinyl alcohol of ethylphenol molar weight 23% between adding, continue to stir the ethylene glycol that adds a hexamethylenetetramine of ethylphenol molar weight 3% and an ethylphenol molar weight 2.5% after 30 minutes, continue to stir 3 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 850 DEG C of charing 1h by room temperature, and then pass into water vapour and activate 2h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon.
Embodiment 2
Between inciting somebody to action, ethylphenol and formaldehyde are that 1:4 is added to the water according to mol ratio, a triethylamine for ethylphenol molar weight 0.75% is added in above-mentioned solution, under the condition stirring, heat to 90 DEG C, then the polyvinyl alcohol of ethylphenol molar weight 23% between adding, continue to stir the polyoxyethylene glycol that adds a hexamethylenetetramine of ethylphenol molar weight 3% and an ethylphenol molar weight 2.8% after 30 minutes, continue to stir 3 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 1000 DEG C of charing 1h by room temperature, and then pass into water vapour and activate 2h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon, its Pore Characteristics is in table 1.
Embodiment 3
Between inciting somebody to action, ethylphenol and formaldehyde are that 1:2 is added to the water according to mol ratio, between inciting somebody to action, ethylphenol molar weight 0.85% triethylamine adds in above-mentioned solution, under the condition stirring, heat to 90 DEG C, then the polyvinyl alcohol of ethylphenol molar weight 23% between adding, continue to stir after 60 minutes and add a hexamethylenetetramine for ethylphenol molar weight 3%, continue to stir 2 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 700 DEG C by room temperature, not charing, and then pass into water vapour and activate 1h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon, its Pore Characteristics is in table 1.
Embodiment 4
Between inciting somebody to action, tert.-butyl phenol and formaldehyde are that 1:6 is added to the water according to mol ratio, an ammoniacal liquor of tert.-butyl phenol molar weight 0.75% is added in above-mentioned solution, under the condition stirring, heat to 90 DEG C, then the sodium laurylsulfonate of tert.-butyl phenol molar weight 30% between adding, continue to stir after 20 minutes and add a trimeric cyanamide for tert.-butyl phenol molar weight 1%, continue to stir 5 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 900 DEG C of charing 1h by room temperature, and then pass into CO
2activate 2h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon, its Pore Characteristics is in table 1.
Embodiment 5
Be that 1:5 is added to the water by 1-naphthols and paraformaldehyde according to mol ratio, the ammoniacal liquor of 1-naphthols molar weight 1% is added in above-mentioned solution, under the condition stirring, heat to 90 DEG C, then add the gum arabic of 1-naphthols molar weight 20%, continue to stir the aniline that adds 1-naphthols molar weight 12% after 30 minutes, the ethylene glycol of 1-naphthols molar weight 15%, continues to stir 3 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 800 DEG C of charing 2h by room temperature, and then pass into CO
2activate 3h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon, its Pore Characteristics is in table 1.
Embodiment 6
Be that 1:2 is added to the water by 1,5-dihydroxy naphthlene and formaldehyde according to mol ratio, by 1, the hydrated barta of 5-dihydroxy naphthlene molar weight 0.8% adds in above-mentioned solution, under the condition stirring, heats to 90 DEG C, then adds 1, the polyvinyl alcohol of 5-dihydroxy naphthlene molar weight 10%, continue to stir the hexamethylenetetramine that adds 1,5-dihydroxy naphthlene molar weight 2% after 30 minutes, 1, the polyoxyethylene glycol of 5-dihydroxy naphthlene molar weight 5%, continue to stir 5 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 900 degrees Celsius of charing 1h by room temperature, and then pass into water vapour and activate 2h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon, its Pore Characteristics is in table 1.
Embodiment 7
Be that 1:3 is added to the water by 1-naphthols and paraformaldehyde according to mol ratio, the triethylamine of 1-naphthols molar weight 10% is added in above-mentioned solution, under the condition stirring, heat to 90 DEG C, then add the gum arabic of 1-naphthols molar weight 30%, continue to stir the trimeric cyanamide that adds 1-naphthols molar weight 1% after 30 minutes, continue to stir 3 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 800 DEG C of charing 2h by room temperature, and then pass into CO
2activate 3h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon, its Pore Characteristics is in table 1.
Embodiment 8
Between inciting somebody to action, ethylphenol and paraformaldehyde are that 1:6 is added to the water according to mol ratio, a triethylamine for ethylphenol molar weight 0.75% is added in above-mentioned solution, under the condition stirring, heat to 90 DEG C, then the polyvinyl alcohol of ethylphenol molar weight 23% between adding, continue to stir the ethylene glycol that adds a hexamethylenetetramine of ethylphenol molar weight 3% and an ethylphenol molar weight 2.5% after 30 minutes, continue to stir 3 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 850 DEG C of charing 1h by room temperature, and then pass into water vapour and activate 2h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon, its Pore Characteristics is in table 1.
Embodiment 9
Be that 1:4 is added to the water by 1,5-dihydroxy naphthlene and paraformaldehyde according to mol ratio, by 1, the triethylamine of 5-dihydroxy naphthlene molar weight 0.8% adds in above-mentioned solution, under the condition stirring, heat to 90 DEG C, then add the polyvinyl alcohol of 1,5-dihydroxy naphthlene molar weight 23%, continue to stir after 30 minutes and add 1, the polyoxyethylene glycol of the hexamethylenetetramine of 5-dihydroxy naphthlene molar weight 3% and 1,5-dihydroxy naphthlene molar weight 5%, continues to stir 3 hours, after cool to room temperature, filter and obtain resin balls.By the resin balls of preparation, under nitrogen protection, be warming up to 850 DEG C of charing 1.5h by room temperature, and then pass into water vapour and activate 1.5h, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon, its Pore Characteristics is in table 1.
Table 1 is prepared the Pore Characteristics of spheric active carbon
Claims (8)
1. a preparation method for the resin base spheric active carbon of controllable hole structure, is characterized in that comprising the steps:
Be that 1:2-6 is added to the water by phenols and aldehydes according to mol ratio, the catalyzer of phenols molar weight 0.7%-1% is added in above-mentioned solution, under the condition stirring, heat to 85-90 DEG C, then add the dispersion agent of phenols molar weight 10%-30%, continue to stir after 20-60 minute and add the solidifying agent of phenols molar weight 1%-3% and the pore-forming material of phenols molar weight 0-5%, continue to stir 2-5 hour, cool to room temperature, filters and obtains resin balls; By the resin balls of preparation, under nitrogen protection, be warming up to 700-1000 DEG C of charing by room temperature, and then pass into carbonic acid gas or water vapour activates, be naturally cooled to room temperature, obtain alkyd resin based spheric active carbon.
2. the preparation method of the resin base spheric active carbon of a kind of controllable hole structure as claimed in claim 1, it is characterized in that described phenols be between ethylphenol, a tert.-butyl phenol, 1-naphthols, 1, one or more mixing in 5-dihydroxy naphthlene.
3. the preparation method of the resin base spheric active carbon of a kind of controllable hole structure as claimed in claim 1, is characterized in that described aldehydes is formaldehyde or paraformaldehyde.
4. the preparation method of the resin base spheric active carbon of a kind of controllable hole structure as claimed in claim 1, is characterized in that described catalyzer is triethylamine, ammoniacal liquor, sodium hydroxide or hydrated barta.
5. the preparation method of the resin base spheric active carbon of a kind of controllable hole structure as claimed in claim 1, is characterized in that described dispersion agent is polyvinyl alcohol, sodium laurylsulfonate or gum arabic.
6. the preparation method of the resin base spheric active carbon of a kind of controllable hole structure as claimed in claim 1, is characterized in that described solidifying agent is hexamethyl tetramine, trimeric cyanamide, aniline; Pore-forming material is polyoxyethylene glycol or ethylene glycol.
7. the preparation method of the resin base spheric active carbon of a kind of controllable hole structure as claimed in claim 1, is characterized in that temperature rise rate 1-5 DEG C/min of described charing, and carbonization time is 0-1h.
8. the preparation method of the resin base spheric active carbon of a kind of controllable hole structure as claimed in claim 1, the activation temperature that it is characterized in that described activation is 700-1000 DEG C, soak time is 1-3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410139231.0A CN103936004B (en) | 2014-04-09 | 2014-04-09 | A kind of preparation method of resin base spheric active carbon of controllable hole structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410139231.0A CN103936004B (en) | 2014-04-09 | 2014-04-09 | A kind of preparation method of resin base spheric active carbon of controllable hole structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103936004A true CN103936004A (en) | 2014-07-23 |
| CN103936004B CN103936004B (en) | 2016-01-20 |
Family
ID=51183932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410139231.0A Active CN103936004B (en) | 2014-04-09 | 2014-04-09 | A kind of preparation method of resin base spheric active carbon of controllable hole structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103936004B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170092A (en) * | 2015-10-23 | 2015-12-23 | 蓝星（成都）新材料有限公司 | Resin-based activated carbon ball and preparation method thereof |
| CN105293488A (en) * | 2015-10-23 | 2016-02-03 | 北京林业大学 | Lignin-based activated carbon microsphere and preparation method and application thereof |
| CN106185919A (en) * | 2016-07-16 | 2016-12-07 | 中国科学院山西煤炭化学研究所 | A kind of method preparing functional resin base spheric active carbon |
| CN107857264A (en) * | 2017-11-08 | 2018-03-30 | 山西新华化工有限责任公司 | Weaken the preparation method of resin base porous carbon material rupture |
| CN108862240A (en) * | 2018-07-31 | 2018-11-23 | 大连理工大学 | A kind of Heteroatom doping charcoal nanosphere and preparation method thereof |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560284A (en) * | 2009-05-04 | 2009-10-21 | 北京索利特新型建筑材料有限公司 | Method for producing foamable phenolic resin and obtained foamable phenolic resin |
| JP2011213571A (en) * | 2010-03-15 | 2011-10-27 | Hiroshima Univ | Spherical carbon material, electricity storage device using the material, method for producing the material, spherical phenol resin, and method for producing the resin |
| CN102659093A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院山西煤炭化学研究所 | Method for preparing mesoporous carbon with narrow pore size distribution |
-
2014
- 2014-04-09 CN CN201410139231.0A patent/CN103936004B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560284A (en) * | 2009-05-04 | 2009-10-21 | 北京索利特新型建筑材料有限公司 | Method for producing foamable phenolic resin and obtained foamable phenolic resin |
| JP2011213571A (en) * | 2010-03-15 | 2011-10-27 | Hiroshima Univ | Spherical carbon material, electricity storage device using the material, method for producing the material, spherical phenol resin, and method for producing the resin |
| CN102659093A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院山西煤炭化学研究所 | Method for preparing mesoporous carbon with narrow pore size distribution |
Non-Patent Citations (2)
| Title |
|---|
| ARJUN SINGH ET AL.: "Microporous Activated Carbon Spheres Prepared from Resole-Type Crosslinked Phenolic Beads by Physical Activation", 《JOURNAL OF APPLIED POLYMER SCIENCE》, vol. 110, 10 September 2008 (2008-09-10) * |
| 杨骏兵等: "添加聚乙二醇对酚醛树脂基球形活性炭结构和性能的影响", 《首届海峡两岸炭材料研讨会》, 7 April 2008 (2008-04-07) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170092A (en) * | 2015-10-23 | 2015-12-23 | 蓝星（成都）新材料有限公司 | Resin-based activated carbon ball and preparation method thereof |
| CN105293488A (en) * | 2015-10-23 | 2016-02-03 | 北京林业大学 | Lignin-based activated carbon microsphere and preparation method and application thereof |
| CN106185919A (en) * | 2016-07-16 | 2016-12-07 | 中国科学院山西煤炭化学研究所 | A kind of method preparing functional resin base spheric active carbon |
| CN106185919B (en) * | 2016-07-16 | 2018-12-21 | 中国科学院山西煤炭化学研究所 | A method of preparing functional resin base spheric active carbon |
| CN107857264A (en) * | 2017-11-08 | 2018-03-30 | 山西新华化工有限责任公司 | Weaken the preparation method of resin base porous carbon material rupture |
| CN108862240A (en) * | 2018-07-31 | 2018-11-23 | 大连理工大学 | A kind of Heteroatom doping charcoal nanosphere and preparation method thereof |
| CN108862240B (en) * | 2018-07-31 | 2021-07-16 | 大连理工大学 | Heteroatom-doped carbon nano-microsphere and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103936004B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103936004B (en) | A kind of preparation method of resin base spheric active carbon of controllable hole structure | |
| CN106185919B (en) | A method of preparing functional resin base spheric active carbon | |
| CN102716716B (en) | Preparation method of activated carbon and alumina composite material | |
| CN103787331A (en) | Preparation method of pitch-based spherical activated carbon with rich meso pores | |
| WO2007095023B1 (en) | Activated carbon monoliths and methods of making them | |
| CN110591419B (en) | Modified superfine carbon black catalyst and application thereof | |
| CN108609602B (en) | Nitrogen-doped microporous carbon material based on energetic polyion liquid and preparation method thereof | |
| EP2687553A1 (en) | Method for producing spherical furfuryl alcohol resin particles, spherical furfuryl alcohol resin particles produced thereby, spherical carbon particles and spherical activated carbon particles | |
| CN104004150A (en) | Bakelite resin capable of generating graphene in in-situ reaction and preparation method thereof | |
| CN102633248A (en) | Preparation method for thermoplastic phenolic resin-based hollow carbon balls | |
| CN101234759A (en) | Method of preparing micropore carbon | |
| CN102689899B (en) | A preparation method for improving specific surface area of activated carbon | |
| CN107199039B (en) | Metallic nickel embedded porous carbon coated honeycomb ceramic monolithic catalyst and application thereof | |
| CN101157451A (en) | Method for preparing resin-based ball charcoal | |
| CN109206636B (en) | Boron-containing phenolic resin hollow microsphere and preparation method thereof | |
| CN102816334B (en) | Superfine phenolic resin powder and preparation method and application thereof | |
| JP2013159515A (en) | Mesoporous carbon gel and method for producing the same | |
| JP2000239335A (en) | High-density cured spherical phenolic resin | |
| CN103908980A (en) | Forming method for spherical particles of molecular sieve catalyst | |
| JP2007091567A (en) | Porous carbon material and its production method | |
| CN114192115B (en) | Preparation method and application of carbon dioxide trapping agent | |
| CN104944374A (en) | Method for low-temperature removal of micro oxycarbide | |
| JP4173061B2 (en) | Method for producing organic polymer gel | |
| CN110066416B (en) | Preparation method of phenolic resin foam and carbon foam | |
| JPS6353154B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |