CN1480398A - Method for preparing spherical active cardon with base of asphaltum riched in mesopores - Google Patents
Method for preparing spherical active cardon with base of asphaltum riched in mesopores Download PDFInfo
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- CN1480398A CN1480398A CNA031785727A CN03178572A CN1480398A CN 1480398 A CN1480398 A CN 1480398A CN A031785727 A CNA031785727 A CN A031785727A CN 03178572 A CN03178572 A CN 03178572A CN 1480398 A CN1480398 A CN 1480398A
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Abstract
A spherical asphalt-base activated carbon rich in mesopores is prepared from petroleum or coking by-product through preparing the asphalt with high softening point, adding arylhydrocarbon and thermosetting phenolic resin, spherisizing, oxidizing, charring and activating.
Description
Technical field: the invention belongs to a kind of preparation method of gac, being specifically related to a kind of is the method for the asphalt-base globular active carbon that is rich in mesopore of feedstock production controllable bore diameter with pitch
Background technology:
Characteristics such as the little and adsorption desorption speed of asphalt-base globular active carbon has good sphericity, physical strength height, fixed bed when using resistance is fast have obtained using widely in fields such as environmental protection, medical treatment, military affairs, chemical industry.Zl97101617.8 and ZL98104975.3 have reported the preparation method of asphalt-base globular active carbon, are raw material with pitch or tar, are properties-correcting agent with the hydrocarbons, adopt the emulsion process balling-up, prepare spheric active carbon by the oxidation carbonization-activation.The rate of oxidation of bitumen ball is decided by oxygen by the speed of surface to internal divergence, and the size and the speed of the hole that rate of diffusion forms when being decided by that hydrocarbons overflows.Because hydrocarbons and pitch and tar solvability are extremely strong, pitch protocorm hydrocarbons when oxidative stabilization is difficult to overflow, and the protocorm oxidation initial stage, still uncured between the asphaltene molecule, along with overflowing of hydrocarbons, bitumen ball is shunk, and is difficult to form primary than macrovoid, rate of oxidation is extremely slow, and energy consumption is very high.The aperture of the asphalt-base globular active carbon that conventional steam activation makes belongs to micropore (less than 2nm) mostly, can obtain the mesopore of a small amount of 2-4nm after the deep activation, but the intensity and the yield of spheric active carbon reduce greatly, this has just limited the range of application of asphalt-base globular active carbon, particularly the application aspect the absorption of liquid phase macromole.ZL98123530.1 has reported a kind of preparation method of mesopore asphalt-base globular active carbon, on Zl97101617.8 and ZL98104975.3 preparation method's basis, adds ferrocene in raw material, promotes the carrying out of priming reaction, forms mesopore activated carbon.ZL99102012.X has reported a kind of method of controlling spheric active carbon, the main method that the follow-up aperture of spheric active carbon is modified that adopts.But aforesaid method still can not avoid the pitch protocorm oxidation initial stage to shrink along with overflowing of hydrocarbons, is difficult to form primary more macroporous drawback, and only reliable follow-up carbonization-activation enlarges the aperture.
Summary of the invention:
The purpose of this invention is to provide the preparation method that a kind of method simply is rich in the asphalt-base globular active carbon of mesopore.
The present invention adopts the method at material asphalt or tar adding self cure pore-creating agent, by surfactant-dispersed, adopts the suspension method balling-up, then by oxidation charing and activation preparation asphalt-base globular active carbon.Concrete steps are as follows: 1. the preparation of high softening point bitumen: with pitch, coal tar, petroleum residual oil or clarified oil is raw material, and at 300-380 ℃ of following bubbling air, oxidation makes its softening temperature reach 200-300 ℃; 2. the preparation of high softening-point modifying asphalt: under 200-350 ℃, in high softening point bitumen, add 15-40Wt% arene small-molecule substance, stir; 3. balling-up bituminous preparation: modifying asphalt is cooled to 80-180 ℃, add the heat-reactive phenolic resin of 2-18Wt% therein, the dispersion agent of 1-5Wt% stirs; 4. the preparation of pitch protocorm: in the polyvinyl alcohol water solution of 1-3Wt% concentration, the 5-40% that presses solution weight adds balling-up pitch, slowly is warming up to 100-200 ℃ under whipped state, cools off under whipped state then, makes the pitch protocorm; 5. the not preparation of molten asphalt ball: pitch protocorm speed with 0.5-5 ℃ in air is warming up to 250-300 ℃, obtains not molten asphalt ball.6. carbonization-activation: the molten asphalt ball is not warming up to 850-1000 ℃ of following charing with the speed of 5-20 ℃/min, feeds steam activation simultaneously, makes asphalt-base globular active carbon.7. aforesaid arene small-molecule substance is naphthalene, methylnaphthalene, anthracene or phenanthrene etc.8. the present invention has following advantage: add the resol with self cure performance in balling-up pitch 9., make it when balling-up or during low-temperature oxidation the crosslinked of self cure and resol and asphaltene molecule can take place, curing reaction has been accelerated the speed of oxidizing reaction in the inner generation of protocorm.10. solidified resol plays the effect of skeleton in bitumen ball, has suppressed the contraction of bitumen ball in oxidising process, makes hydrocarbons keep certain hole when overflowing, and has promoted the carrying out of oxidizing reaction, and cost is low.11. for pitch, resol charcoal yield in carbonization process is low, is easy to decompose, obstructed overactivation also can form relatively abundanter hole, helps entering of activated gas, has significantly reduced the activatory time.12. utilize the pore effect of resol when charing, by the add-on of control resol, can control the pore structure of spheric active carbon, be easy in the time of especially prepare the spheric active carbon that is rich in large pore, improved product properties.
Embodiment:
Embodiment 1:
With softening temperature is that 105 ℃ modified pitch is a raw material, and preparing softening temperature 300 ℃ of following oxidations is 250 ℃ pitch.Add the 15Wt% naphthalene down at 270 ℃, stir.Above-mentioned pitch is cooled to 180 ℃, add the heat-reactive phenolic resin 213 of 2Wt% therein, the polyethylene of dispersing agent alcohol of 1Wt% stirs.In the polyvinyl alcohol water solution of 1% concentration, add the balling-up pitch of 5Wt%, under whipped state, slowly be warming up to 200 ℃, under whipped state, cool off then, make the pitch protocorm.Pitch protocorm speed with 0.5 ℃/min in air is warming up to 300 ℃, obtains not molten asphalt ball.Will be not in the fluidized-bed activated reactor molten asphalt ball be warming up to 850 ℃ of following charings with the speed of 10 ℃/min, feed steam activation simultaneously, make asphalt-base globular active carbon.The performance of asphalt-base globular active carbon sees Table 1.
Embodiment 2
As the method for embodiment 1, the preparation softening temperature is 300 ℃ a pitch, at 270 ℃ of dimethylnaphthalenes that add 40Wt% down, stirs.Above-mentioned pitch is cooled to 180 ℃, add the heat-reactive phenolic resin 214 of 18Wt% therein, the dispersion agent carboxymethyl cellulose of 5Wt% stirs.In the polyvinyl alcohol water solution of 5% concentration, add the balling-up pitch of 40Wt%, under whipped state, slowly be warming up to 180 ℃, under whipped state, cool off then, make the pitch protocorm.Pitch protocorm speed with 5 ℃/min in air is warming up to 300 ℃, obtains not molten asphalt ball.Will be not in the fluidized-bed activated reactor molten asphalt ball be warming up to 1000 ℃ of following charings with the speed of 10 ℃/min, feed steam activation simultaneously, make asphalt-base globular active carbon.The performance of asphalt-base globular active carbon sees Table 1.
Embodiment 3
As the method for embodiment 1, the preparation softening temperature is 230 ℃ a pitch, adds 30% dimethylnaphthalene under 200 ℃, stirs.Above-mentioned pitch is cooled to 80 ℃, add the heat-reactive phenolic resin 213 of 8Wt% therein, the dispersion agent carboxymethyl cellulose of 3Wt% stirs.In the polyvinyl alcohol water solution of 2% concentration, add the balling-up pitch of 30Wt%, under whipped state, slowly be warming up to 100 ℃, under whipped state, cool off then, make the pitch protocorm.Pitch protocorm speed with 3 ℃/min in air is warming up to 280 ℃, obtains not molten asphalt ball.Will be not in the fluidized-bed activated reactor molten asphalt ball be warming up to 900 ℃ of following charings with the speed of 8 ℃/min, feed steam activation simultaneously, make asphalt-base globular active carbon.The performance of asphalt-base globular active carbon sees Table 1.
Embodiment 4
With heat-reactive phenolic resin 214 quantitative changes in embodiment 2 methods is 12Wt%, and becoming bulb temperature is 170 ℃, and other condition is identical.
Embodiment 5
With heat-reactive phenolic resin 213 quantitative changes in embodiment 3 methods is 5Wt%, and becoming bulb temperature is 120 ℃, and other condition is identical.The performance of asphalt-base globular active carbon sees Table 1.
Comparative Examples 1
Embodiment 1 does not add resol and dispersion agent, and other condition is identical, the preparation spheric active carbon.The performance of asphalt-base globular active carbon sees Table 1.
Comparative Examples 2
Embodiment 3 does not add resol and dispersion agent, and other condition is identical, the preparation spheric active carbon.The performance of asphalt-base globular active carbon sees Table 1.
Table 1:
| Sample | Outward appearance | BET specific surface area (m 2/g) | Total pore volume (ml/g) | Non-micropore pore volume (ml/g) | Non-micropore ratio (%) |
| Embodiment 1 | More smooth | ????1198 | ????0.79 | ?????0.32 | ????40 |
| Embodiment 2 | More smooth | ????1248 | ????0.93 | ?????0.65 | ????70 |
| Embodiment 3 | Smooth | ????1230 | ????0.83 | ?????0.50 | ????61 |
| Embodiment 4 | Smooth | ????1399 | ????0.87 | ?????0.55 | ????64 |
| Embodiment 5 | Smooth | ????1042 | ????0.80 | ?????0.46 | ????57 |
| Comparative Examples 1 | Smooth | ????871 | ????0.43 | ?????0.08 | ????19 |
| Comparative Examples 2 | Part is melted also | ????950 | ????0.47 | ?????0.11 | ????23 |
Claims (2)
1. a preparation method who is rich in the asphalt-base globular active carbon of mesopore is characterized in that comprising the steps:
(1) preparation of high softening point bitumen: with pitch, coal tar, petroleum residual oil or clarified oil is raw material, and at 300-380 ℃ of following bubbling air, oxidation makes its softening temperature reach 200-300 ℃;
(2) preparation of high softening-point modifying asphalt: under 200-350 ℃, in high softening point bitumen, add 15-40Wt% arene small-molecule substance, stir;
(3) balling-up bituminous preparation: modifying asphalt is cooled to 80-180 ℃, add the heat-reactive phenolic resin of 2-18Wt% therein, the dispersion agent of 1-5Wt% stirs;
(4) preparation of pitch protocorm: in the polyvinyl alcohol water solution of 1-3Wt% concentration, the 5-40% that presses solution weight adds balling-up pitch, slowly is warming up to 100-200 ℃ under whipped state, cools off under whipped state then, makes the pitch protocorm;
(5) the not preparation of molten asphalt ball: pitch protocorm speed with 0.5-5 ℃ in air is warming up to 250-300 ℃, obtains not molten asphalt ball.
(6) carbonization-activation: the molten asphalt ball is not warming up to 850-1000 ℃ of following charing with the speed of 5-20 ℃/min, feeds steam activation simultaneously, makes asphalt-base globular active carbon.
2. a kind of preparation method who is rich in the asphalt-base globular active carbon of mesopore as claimed in claim 1 is characterized in that described arene small-molecule substance is naphthalene, methylnaphthalene, anthracene or phenanthrene.
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| CNB031785727A CN1247453C (en) | 2003-07-18 | 2003-07-18 | Method for preparing spherical active cardon with base of asphaltum riched in mesopores |
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| CNB031785727A CN1247453C (en) | 2003-07-18 | 2003-07-18 | Method for preparing spherical active cardon with base of asphaltum riched in mesopores |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344533C (en) * | 2005-12-27 | 2007-10-24 | 中国科学院山西煤炭化学研究所 | Process for preparing high strength carbon/graphite material |
| CN101792678A (en) * | 2010-04-07 | 2010-08-04 | 中国海洋石油总公司 | Preparation method of bitumen balls |
| CN1938226B (en) * | 2004-04-02 | 2010-11-03 | 株式会社吴羽 | Method for producing spherical activated carbon |
| CN103289719A (en) * | 2013-06-08 | 2013-09-11 | 中国科学院山西煤炭化学研究所 | Process for preparing asphalt sphere |
| CN103787331A (en) * | 2014-02-28 | 2014-05-14 | 东北林业大学 | Preparation method of pitch-based spherical activated carbon with rich meso pores |
| CN104030287A (en) * | 2014-07-09 | 2014-09-10 | 四川创越炭材料有限公司 | Spherical activated carbon and preparation method thereof |
| CN104261406A (en) * | 2014-09-25 | 2015-01-07 | 四川创越炭材料有限公司 | Asphalt-based mesoporous spherical activated carbon and preparation method thereof |
| CN106744933A (en) * | 2016-11-16 | 2017-05-31 | 俞祥敏 | A kind of preparation method for being adapted to industrial asphalt-base spherical activated carbon |
| CN108940134A (en) * | 2018-06-20 | 2018-12-07 | 东南大学 | Coal pitch spheres aoxidize infusible continuous reaction apparatus and method |
| CN109052397A (en) * | 2018-09-25 | 2018-12-21 | 湖南曦威新材料有限公司 | A kind of preparation method with hierarchical pore structure asphalt-base spherical activated carbon |
| CN109609167A (en) * | 2018-11-30 | 2019-04-12 | 中国科学院山西煤炭化学研究所 | A method of promoting the pitch quickly oxidative stabilization of homogeneous |
| CN111547721A (en) * | 2020-05-09 | 2020-08-18 | 中国铝业股份有限公司 | Preparation method of mesoporous activated carbon for supercapacitor |
-
2003
- 2003-07-18 CN CNB031785727A patent/CN1247453C/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938226B (en) * | 2004-04-02 | 2010-11-03 | 株式会社吴羽 | Method for producing spherical activated carbon |
| CN100344533C (en) * | 2005-12-27 | 2007-10-24 | 中国科学院山西煤炭化学研究所 | Process for preparing high strength carbon/graphite material |
| CN101792678A (en) * | 2010-04-07 | 2010-08-04 | 中国海洋石油总公司 | Preparation method of bitumen balls |
| CN103289719B (en) * | 2013-06-08 | 2014-11-26 | 中国科学院山西煤炭化学研究所 | Process for preparing asphalt sphere |
| CN103289719A (en) * | 2013-06-08 | 2013-09-11 | 中国科学院山西煤炭化学研究所 | Process for preparing asphalt sphere |
| CN103787331A (en) * | 2014-02-28 | 2014-05-14 | 东北林业大学 | Preparation method of pitch-based spherical activated carbon with rich meso pores |
| CN104030287A (en) * | 2014-07-09 | 2014-09-10 | 四川创越炭材料有限公司 | Spherical activated carbon and preparation method thereof |
| CN104030287B (en) * | 2014-07-09 | 2015-11-18 | 四川创越炭材料有限公司 | A kind of spheric active carbon and preparation method thereof |
| CN104261406A (en) * | 2014-09-25 | 2015-01-07 | 四川创越炭材料有限公司 | Asphalt-based mesoporous spherical activated carbon and preparation method thereof |
| CN106744933A (en) * | 2016-11-16 | 2017-05-31 | 俞祥敏 | A kind of preparation method for being adapted to industrial asphalt-base spherical activated carbon |
| CN108940134A (en) * | 2018-06-20 | 2018-12-07 | 东南大学 | Coal pitch spheres aoxidize infusible continuous reaction apparatus and method |
| CN109052397A (en) * | 2018-09-25 | 2018-12-21 | 湖南曦威新材料有限公司 | A kind of preparation method with hierarchical pore structure asphalt-base spherical activated carbon |
| CN109052397B (en) * | 2018-09-25 | 2021-12-03 | 湖南曦威新材料有限公司 | Preparation method of asphalt-based spherical activated carbon with hierarchical pore structure |
| CN109609167A (en) * | 2018-11-30 | 2019-04-12 | 中国科学院山西煤炭化学研究所 | A method of promoting the pitch quickly oxidative stabilization of homogeneous |
| CN111547721A (en) * | 2020-05-09 | 2020-08-18 | 中国铝业股份有限公司 | Preparation method of mesoporous activated carbon for supercapacitor |
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| CN1247453C (en) | 2006-03-29 |
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