CN1102427C - Process for preparing sphrical activated carbon by adding pore-forming agent - Google Patents
Process for preparing sphrical activated carbon by adding pore-forming agent Download PDFInfo
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- CN1102427C CN1102427C CN99110071A CN99110071A CN1102427C CN 1102427 C CN1102427 C CN 1102427C CN 99110071 A CN99110071 A CN 99110071A CN 99110071 A CN99110071 A CN 99110071A CN 1102427 C CN1102427 C CN 1102427C
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- Prior art keywords
- resin
- activated carbon
- dispersion
- pore
- forming agent
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 229920003986 novolac Polymers 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000005011 phenolic resin Substances 0.000 claims description 21
- 229920001568 phenolic resin Polymers 0.000 claims description 17
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 12
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 241000978776 Senegalia senegal Species 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 239000002612 dispersion medium Substances 0.000 claims 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 238000003763 carbonization Methods 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- -1 polyoxymethylene Polymers 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000008247 solid mixture Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000010000 carbonizing Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 230000004913 activation Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000013467 fragmentation Methods 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- FTDXCHCAMNRNNY-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1 FTDXCHCAMNRNNY-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
一种添加造孔剂制备球形活性炭的方法，以线型酚醛树脂为原料，在成球之前加入固化剂和有机造孔剂，经乳化成球，炭化和活化制备出球形活性炭。本方法工艺简单，易操作，可以得到比表面较大且非微孔比例高的球形活性炭。A method for preparing spherical activated carbon by adding a pore-forming agent, using novolac resin as a raw material, adding a curing agent and an organic pore-forming agent before forming into balls, emulsifying into balls, carbonizing and activating to prepare spherical activated carbon. The method has simple process and is easy to operate, and can obtain spherical activated carbon with large specific surface and high proportion of non-micropores.
Description
The invention belongs to preparation method of active carbon, relate in particular to a kind of method that pore creating material prepares spherical activated charcoal of adding.
Spherical activated charcoal is owing to have good sphericity and higher mechanical strength, loading density is even when fixed bed uses, the convection cell resistance is little, the big adsorption rate of its adsorption capacity is fast simultaneously, so obtained in fields such as industry, agricultural, military affairs using widely as adsorption and separation material, catalysis material, electronic energy source material, biological engineering material.Chinese patent application 98115717.3 has provided a kind of preparation method of phenolic resin base globe activated char, and its process route is as follows:
1. linear phenol-aldehyde resin and curing agent are mixed, obtain material resin;
2. material resin is distributed to emulsion process balling-up in the dispersion liquid;
3. resulting spherical phenolic resins is carried out conventional charing and activation, obtain phenolic resin base globe activated char.
The character of phenolic resins itself determined that this spherical activated charcoal is in the majority with micropore, and specific area is less.
Goal of the invention of the present invention provides a kind of preparation method with bigger serface, phenolic resin base globe activated char that non-micropore ratio is high.
The object of the present invention is achieved like this, is raw material with the linear phenol-aldehyde resin, added curing agent and pore creating material before balling-up, and through the emulsification balling-up, spherical activated charcoal is prepared in charing and activation.Concrete steps are as follows:
(1) linear phenol-aldehyde resin, pore creating material and curing agent are mixed in organic solvent, decompression is steamed down and is desolventized, and obtains solid mixt, again through being crushed to 0.45-1.25mm, obtains material resin;
(2) with material resin by following weight ratio: material resin: decentralized medium=(5-10): 100 join in the dispersion liquid, slowly be warmed up to 90-130 ℃ and form resin microsphere under at the uniform velocity stirring, wherein dispersion liquid is by dispersant: decentralized medium=(2-10): 100 weight ratios are made into;
(3) ball that become being warmed up to 600-1000 ℃ with the speed of (1-20) ℃/min under inert atmosphere carries out charing and handles;
(4) under 700-900 ℃, utilize water vapour to carry out activation processing in the ball after the charing, obtain phenolic resin base globe activated char;
Aforesaid linear phenol-aldehyde resin is common thermoplastic novolac phenolic resin, can be generated by excessive phenol and aldehyde reaction under acid catalysis.Its softening point is 60-120 ℃, but the most suitable phenolic resins of the present invention is 90-120 ℃;
Aforesaid curing agent is hexamethylenetetramine, polyformaldehyde; But the most suitable curing agent of the present invention is a hexamethylenetetramine;
Aforesaid decentralized medium is water, glycerine and silicone oil, but the most suitable decentralized medium of the present invention is a water;
Aforesaid dispersant is lauryl sodium sulfate, emulsifying agent-EL90 and gum arabic;
It is characterized in that: the weight ratio of balling-up raw material is: linear phenol-aldehyde resin: pore creating material: curing agent: organic solvent=100: (5-25): (7-25): (200-500).
Described pore creating material is a polyethylene glycol.
Since added organic pore-forming agents in the raw material, so the spherical activated charcoal that obtains has bigger specific area, and non-micropore ratio height.
Embodiments of the invention are as follows:
Embodiment 1
(1) be that 1000 polyethylene glycol, 11 gram hexamethylenetetramines and 200ml absolute methanol add reactor together with 100 gram linear phenol-aldehyde resins, 5 gram-molecular weights, under 55 ℃, at the uniform velocity stirred 120 minutes, linear phenol-aldehyde resin, polyethylene glycol and hexamethylenetetramine are dissolved fully, then mixed liquor is under reduced pressure steamed except that methyl alcohol, obtain solid mixt, obtain after the fragmentation particle diameter between 0.45-1.25mm, be suitable for preparing the material resin of phenol phenol resin base globe activated char.
(2) in autoclave, add 1000ml water, 32 gram lauryl sodium sulfate, after stirring material resin 50 grams that obtain in the step 1 are added, at the uniform velocity stir down and slowly be warmed up to 125 ℃, keep stirring that reactor is cooled off naturally, obtain the spherical phenolic resins of particle diameter between 0.45-1.25mm.
(3) the spherical phenolic resins that obtains in the step 2 is heated to 800 ℃ and be incubated 30 minutes and carry out charing with the speed of 2 ℃/min under nitrogen protection.
(4) the phenolic resin based spherical charcoal that obtains in the step 3 is heated to 800 ℃ with the speed of 10 ℃/min, fed steam activation 90 minutes, obtain phenolic resin base globe activated char.The results are shown in Table 1.
Embodiment 2
(1) be that 6000 polyethylene glycol, 11 gram hexamethylenetetramines and 250ml absolute methanol add reactor together with 100 gram linear phenol-aldehyde resins, 15 gram-molecular weights, under 55 ℃, at the uniform velocity stirred 120 minutes, linear phenol-aldehyde resin, polyethylene glycol and hexamethylenetetramine are dissolved fully, then mixed liquor is under reduced pressure steamed except that methyl alcohol, obtain solid mixt, obtain after the fragmentation particle diameter between 0.45-1.25mm, be suitable for preparing the material resin of phenol phenol resin base globe activated char.
Carry out emulsification balling-up, charing and activation as step 2,3,4 pairs of above-mentioned raw materials resins among the embodiment 1, obtain phenolic resin base globe activated char.The results are shown in Table 1.
Embodiment 3
(1) be that 2000 polyethylene glycol, 11 gram hexamethylenetetramines and 200ml absolute methanol add reactor together with 100 gram linear phenol-aldehyde resins, 25 gram-molecular weights, under 55 ℃, at the uniform velocity stirred 120 minutes, linear phenol-aldehyde resin, polyethylene glycol and hexamethylenetetramine are dissolved fully, then mixed liquor is under reduced pressure steamed except that methyl alcohol, obtain solid mixt, obtain after the fragmentation particle diameter between 0.45-1.25mm, be suitable for preparing the material resin of phenol phenol resin base globe activated char.
Carry out emulsification balling-up, charing and activation as step 2,3,4 pairs of above-mentioned raw materials resins among the embodiment 1, obtain phenolic resin base globe activated char.The results are shown in Table 1.
Comparative Examples
100 gram linear phenol-aldehyde resins, 11 gram hexamethylenetetramines and 200ml absolute alcohol are added reactor together, under 55 ℃, at the uniform velocity stirred 60 minutes, linear phenol-aldehyde resin and hexamethylenetetramine are dissolved fully, then mixed liquor is under reduced pressure steamed except that methyl alcohol, obtain solid mixt, obtain after the fragmentation particle diameter between 0.45-1.25mm, be suitable for preparing the material resin of phenol phenol resin base globe activated char.
Carry out emulsification balling-up, charing and activation as step 2,3,4 pairs of above-mentioned raw materials resins among the embodiment 1, obtain phenolic resin base globe activated char.The results are shown in Table 1.The specific area of the phenolic resin base globe activated char of table 1 gained and pore structure data
| Project | BET specific area (m 2/g) | Non-micropore specific area (m 2/g) | Non-micropore specific area/total specific area (%) | Total pore volume cm 3/g | Non-micropore pore volume (cm 3/g) | Non-micropore pore volume/total pore volume (%) |
| Comparative Examples | 905 | 120 | 13.3 | 0.442 | 0.074 | 16.7 |
| Embodiment 1 | 1176 | 191 | 16.2 | 0.513 | 0.116 | 22.6 |
| Embodiment 2 | 1107 | 288 | 20.5 | 0.616 | 0.266 | 26 9 |
| Embodiment 3 | 1663 | 470 | 28.3 | 0.773 | 0.291 | 37.6 |
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110071A CN1102427C (en) | 1999-06-30 | 1999-06-30 | Process for preparing sphrical activated carbon by adding pore-forming agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110071A CN1102427C (en) | 1999-06-30 | 1999-06-30 | Process for preparing sphrical activated carbon by adding pore-forming agent |
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| Publication Number | Publication Date |
|---|---|
| CN1279125A CN1279125A (en) | 2001-01-10 |
| CN1102427C true CN1102427C (en) | 2003-03-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99110071A Expired - Fee Related CN1102427C (en) | 1999-06-30 | 1999-06-30 | Process for preparing sphrical activated carbon by adding pore-forming agent |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100563478C (en) | 2003-03-07 | 2009-12-02 | 弗吉尼亚联邦大学 | Phenolic materials and methods for electrical machining |
| US8247072B2 (en) | 2006-02-14 | 2012-08-21 | Eastman Chemical Company | Resol beads, methods of making them and methods of using them |
| CN100528747C (en) * | 2007-02-07 | 2009-08-19 | 中国科学院山西煤炭化学研究所 | Method for preparing medium pore carbon of narrow aperture and high degree of graphitization |
| CN101983918B (en) * | 2010-11-25 | 2012-05-30 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of millimeter-scale activated carbon pellet |
| CN102874806B (en) * | 2012-09-26 | 2014-08-20 | 中国科学院山西煤炭化学研究所 | Preparation method for spherical activated carbon with high bulk density and high specific surface area |
| CN103253664B (en) * | 2013-06-05 | 2015-04-15 | 山东省科学院能源研究所 | Method for preparing activated carbon |
| CN103880006B (en) * | 2014-03-13 | 2015-06-24 | 常州中科海纳碳素科技有限公司 | Method for preparing large particle size phenolic resin spherical activated carbon |
| CN106185918A (en) * | 2016-07-19 | 2016-12-07 | 句容市百诚活性炭有限公司 | A kind of preparation method of the activated carbon of hierarchical porous structure |
| CN106328390A (en) * | 2016-08-30 | 2017-01-11 | 中国科学院山西煤炭化学研究所 | Method for preparing active carbon microspheres with high specific capacitance in large scale |
| CN107213878A (en) * | 2017-05-31 | 2017-09-29 | 江苏精盾节能科技有限公司 | A kind of modified adsorbent and preparation method thereof |
| CN110075791A (en) * | 2019-04-04 | 2019-08-02 | 河南嘉利美环保材料有限公司 | A kind of complex spherical active carbon purifying particle and preparation method thereof |
| CN111099574A (en) * | 2019-12-27 | 2020-05-05 | 浙江大学 | Preparation method of hierarchical porous carbon aerogel for negative electrode of lithium ion battery |
| CN117923467B (en) * | 2024-03-21 | 2024-06-28 | 中国科学院金属研究所 | A kind of carbon aerogel microsphere and its preparation method and application |
| CN119263273B (en) * | 2024-10-30 | 2025-05-30 | 北京壹金新能源科技有限公司 | Preparation method of anti-loss porous carbon material for silicon-carbon negative electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0543348A (en) * | 1991-08-06 | 1993-02-23 | Mitsui Petrochem Ind Ltd | Method for producing activated carbon porous material |
| JPH05170566A (en) * | 1991-12-25 | 1993-07-09 | Mitsui Petrochem Ind Ltd | Method for producing activated carbon porous structure |
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1999
- 1999-06-30 CN CN99110071A patent/CN1102427C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0543348A (en) * | 1991-08-06 | 1993-02-23 | Mitsui Petrochem Ind Ltd | Method for producing activated carbon porous material |
| JPH05170566A (en) * | 1991-12-25 | 1993-07-09 | Mitsui Petrochem Ind Ltd | Method for producing activated carbon porous structure |
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| CN1279125A (en) | 2001-01-10 |
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