CN1559891A - Preparation process of porous phenolic resin group charring microball - Google Patents
Preparation process of porous phenolic resin group charring microball Download PDFInfo
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- CN1559891A CN1559891A CNA2004100167025A CN200410016702A CN1559891A CN 1559891 A CN1559891 A CN 1559891A CN A2004100167025 A CNA2004100167025 A CN A2004100167025A CN 200410016702 A CN200410016702 A CN 200410016702A CN 1559891 A CN1559891 A CN 1559891A
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- resol
- tensio
- based carbon
- active agent
- constant temperature
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Abstract
The invention discloses a mulitporous phenolics based carbon mcirosphere preparing method, including the following steps: mixing the alcohol solution of resol with the water solution of surfactant to form a uniform emulsion, stirring and solidifying at temperature of 100 deg.C-50 deg.C, then heating to 800 deg.C-1200 deg.C at a temperature ascending speed of 5 deg.C-10 deg.C/min, keeping constant temperature for 0.5-1 hour and carbonizing, and cooling to obtain the phenolics-based carbon mcirospheres. It has cheap raw materials, simple technique, high yield, good sphericity, controllable sphere diameter and specific surface area.
Description
Technical field
The present invention relates to a kind of charcoal preparation methods, relate in particular to a kind of preparation method of expanded phenol-formaldehyde resin based carbon microsphere.
Background technology
The expanded phenol-formaldehyde resin based carbon microsphere is a kind of gas adsorption and storage art of being widely used in, and the potential application prospect is arranged aspect super capacitor material.
(the plain technology of charcoal such as Yang Junbing were once arranged, 2000,109 (4): 36) reported that employing resol prepares the method for the ball shape active carbon of diameter about 2mm, related method is owing to have the ten minutes confidential relation with the mixing of solidifying agent, pore-creating agent and resol, fragmentation, screening, so loss is big, cost is high.And sphere diameter is big, must increase diffusion process, influences result of use.
Since the MCMB invention, constantly the someone is devoted to the preparation of micron-sized isotropy carbon microspheres.For example KOMADA etc. (carbon, 1991,29:43) be reported in the method for heating micron order asphalt powder in the silicone oil.Because asphalt powder is dispersed bad in silicone oil, is easy to reunite in heat-processed, sphericity is poor, specific surface area is difficult to control.
The technical issues that need to address of the present invention are the preparation methods that disclose a kind of expanded phenol-formaldehyde resin based carbon microsphere, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
Aqueous solution with the ethanolic soln and the tensio-active agent of resole forms uniform milk sap, under the temperature of the pressure of 0.1～1.5MPa and 100～150 ℃, stirs and solidifies 0.5～5 hour then, collects the resol microballoon;
Again with the resol microballoon addressed 50～110 ℃ of oven dry down, be heated to 800～1200 ℃ with the heat-up rate of 5～10 ℃/min, constant temperature carried out charing in 0.1～5 hour, obtained said resol based carbon microsphere after the cooling.
Said resole is called heat-reactive phenolic resin again, can adopt conventional method to be prepared or to adopt the commercially available prod;
Said tensio-active agent preferably adopts a kind of or its mixture in polyvinyl alcohol (PVA), cetyl dimethyl amine oxide or the hexadecyl brometo de amonio;
The sphere diameter of resol based carbon microsphere of the present invention can be by resole the concentration of ethanolic soln control, the weight percent concentration of resole is 30～95% in the ethanolic soln, preferred concentration is 50～90%, with this understanding, the sphere diameter of the resol based carbon microsphere that is obtained is 5～150um, when the concentration of resole when 90.0wt% drops to 50.0wt%, the diameter of resulting micron ball charcoal is reduced to 8um from 90um.
The specific surface area of resol based carbon microsphere of the present invention then can be controlled by heating rate, heating rate is high more, then solidification rate is fast more, specific surface area is high more, therefore generally be controlled at 0.5～20 ℃/min, preferably be controlled at 1～15 ℃/min, when solidifying heat-up rate when 10 ℃/min is reduced to 1.0 ℃/min, specific surface area is from 583m
2/ g is reduced to 31m
2/ g.
The volume ratio of the ethanolic soln of resole and the aqueous solution of tensio-active agent is 1: 1～1: 10.
The present invention has following advantage: cost of material is cheap, and technology is simple, the yield height, and good sphericity, sphere diameter and controllable specific surface area are convenient to industrializing implementation.
Description of drawings
Fig. 1 is the electromicroscopic photograph of resol based carbon microsphere
Embodiment
Embodiment 1
In 100ml concentration is that adding 100ml concentration is the resole ethanolic soln of 90.0wt% in the 1.0wt%PVA aqueous solution, and the heat-up rate with 10.0 ℃/min in the high pressure stirring tank is heated to 120 ℃, and pressure is 1.0, constant temperature 3 hours.Cooled and filtered.Filter cake is dry under 110 ℃, and the speed with 10 ℃/min is warmed up to 1000 ℃ under nitrogen protection, and constant temperature 15min obtains the resol based carbon microsphere.Average ball diameter is 90.0um, and specific surface area is 520m
2/ g.Its electromicroscopic photograph such as Fig. 1.As seen from Figure 1, the resol based carbon microsphere good sphericity that is obtained, particle diameter is respectively evenly.
Embodiment 2
In 100ml concentration is that adding 100ml concentration is the resole ethanolic soln of 85.0wt% in the 1.0wt%PVA aqueous solution, and the heat-up rate with 10.0 ℃/min in the high pressure stirring tank is heated to 110 ℃, and pressure is 0.9, constant temperature 3 hours.Cooled and filtered.Filter cake is dry under 110 ℃, and the speed with 10 ℃/min is warmed up to 1200 ℃ under nitrogen protection, and constant temperature 15min obtains the resol based carbon microsphere.Average ball diameter is 18.0um, and specific surface area is 536m
2/ g.
Embodiment 3
In 100ml concentration is that adding 100ml concentration is the resol ethanolic soln of 66.0wt% in the 1.0wt%PVA aqueous solution, and the heat-up rate with 10.0 ℃ in the high pressure stirring tank is heated to 120 ℃, constant temperature 3 hours.Cooled and filtered.Filter cake is dry under 110 ℃, and the speed with 10 ℃/min is warmed up to 1000 ℃ under nitrogen protection, and constant temperature 15min obtains the resol based carbon microsphere.Average ball diameter is 10.0um, and specific surface area is 566m
2/ g.
Embodiment 4
In 100ml concentration is that adding 100ml concentration is the resol ethanolic soln of 50.0wt% in the 1.0wt%PVA aqueous solution, and the heat-up rate with 10.0 ℃/min in the high pressure stirring tank is heated to 120 ℃, constant temperature 3 hours.Cooled and filtered.Filter cake is dry under 110 ℃, and the speed with 10 ℃/min is warmed up to 1000 ℃ under nitrogen protection, and constant temperature 15min obtains the resol based carbon microsphere.Average ball diameter is 8.0um, and specific surface area is 583m
2/ g.
Embodiment 5
In 100ml concentration is that adding 100ml concentration is the resol ethanolic soln of 66.0wt% in the 1.0wt%PVA aqueous solution, and the heat-up rate with 5.0 ℃/min in the high pressure stirring tank is heated to 120 ℃, constant temperature 3 hours.Cooled and filtered.Filter cake is dry under 110 ℃, and the speed with 10 ℃/min is warmed up to 1000 ℃ under nitrogen protection, and constant temperature 15min obtains the resol based carbon microsphere.Average ball diameter is 10.0um, and specific surface area is 325m
2/ g.
Embodiment 6
In 100ml concentration is that adding 100ml concentration is the resol ethanolic soln of 66.0wt% in the 1.0wt%PVA aqueous solution, and the heat-up rate with 1.0 ℃/min in the high pressure stirring tank is heated to 120 ℃, constant temperature 3 hours.Cooled and filtered.Filter cake is dry under 110 ℃, and the speed with 10 ℃/min is warmed up to 1000 ℃ under nitrogen protection, and constant temperature 15min obtains the resol based carbon microsphere.Average ball diameter is 10.0um, and specific surface area is 31m
2/ g.
Claims (7)
1. the preparation method of an expanded phenol-formaldehyde resin based carbon microsphere, it is characterized in that, comprise the steps: the ethanolic soln of resole is mixed with the aqueous solution tensio-active agent of tensio-active agent, form milk sap, be warmed up under 100～150 ℃ the temperature with 1-15 ℃/min then, solidified 0.5～5 hour, and collected the resol microballoon; Again the resol microballoon addressed is heated to 800～1200 ℃ with the heat-up rate of 5～10 ℃/min, the constant temperature charing obtains said resol based carbon microsphere after the cooling.
2. method according to claim 1 is characterized in that, the resol microballoon of being addressed is dried the back charings down at 50～110 ℃.
3. method according to claim 1 is characterized in that, constant temperature carried out charing in 0.1～5 hour.
4. method according to claim 1 is characterized in that, stirs to solidify 0.5～5 hour.
5. according to each described method of claim 1～4, it is characterized in that the volume ratio of the ethanolic soln of resole and the aqueous solution of tensio-active agent is 1: 1～1: 10.
6. according to each described method of claim 1～4, it is characterized in that said tensio-active agent adopts a kind of or its mixture in polyvinyl alcohol (PVA), cetyl dimethyl amine oxide or the hexadecyl brometo de amonio.
7. method according to claim 6 is characterized in that, the volume ratio of the ethanolic soln of resole and the aqueous solution of tensio-active agent is 1: 1～1: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100167025A CN1559891A (en) | 2004-03-03 | 2004-03-03 | Preparation process of porous phenolic resin group charring microball |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100167025A CN1559891A (en) | 2004-03-03 | 2004-03-03 | Preparation process of porous phenolic resin group charring microball |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830457A (en) * | 2010-05-20 | 2010-09-15 | 湖南大学 | Method for preparing carbon microspheres and application of heteropolyacid in carbon microsphere preparation and graphitization |
| CN101157451B (en) * | 2007-09-16 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Method for preparing resin-based ball charcoal |
| CN102816334A (en) * | 2011-06-10 | 2012-12-12 | 中国科学院金属研究所 | Superfine phenolic resin powder and preparation method and application thereof |
| CN103508437A (en) * | 2013-08-13 | 2014-01-15 | 南京工业大学 | Preparation method of phenolic resin base glass carbon microsphere |
-
2004
- 2004-03-03 CN CNA2004100167025A patent/CN1559891A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157451B (en) * | 2007-09-16 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Method for preparing resin-based ball charcoal |
| CN101830457A (en) * | 2010-05-20 | 2010-09-15 | 湖南大学 | Method for preparing carbon microspheres and application of heteropolyacid in carbon microsphere preparation and graphitization |
| CN102816334A (en) * | 2011-06-10 | 2012-12-12 | 中国科学院金属研究所 | Superfine phenolic resin powder and preparation method and application thereof |
| CN103508437A (en) * | 2013-08-13 | 2014-01-15 | 南京工业大学 | Preparation method of phenolic resin base glass carbon microsphere |
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