CN1583550A - Preparing method for porous carbon with high specific surface area - Google Patents
Preparing method for porous carbon with high specific surface area Download PDFInfo
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- CN1583550A CN1583550A CN 200410012345 CN200410012345A CN1583550A CN 1583550 A CN1583550 A CN 1583550A CN 200410012345 CN200410012345 CN 200410012345 CN 200410012345 A CN200410012345 A CN 200410012345A CN 1583550 A CN1583550 A CN 1583550A
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- specific surface
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Abstract
A mesoporous charcoal with high specific surface area is prepared through dissolving KOH in water, immersing microporous charcoal in it, heating in inertial gas, constant-temp reaction, natural cooling, and water washing.
Description
Technical field
The invention belongs to a kind of preparation method of porous charcoal, relate in particular to a kind of preparation method of high-specific surface area mesopore charcoal.
Background technology
Porous charcoal is because its raw material sources are abundant, cheap, and is applied to many fields such as environment, medical science, the energy.Yet different Application Areass requires also to be not quite similar to the technical parameter of porous charcoal.As electrode material for super capacitor, though the micropore charcoal has the specific surface area of superelevation, but owing to its aperture little (2nm following) is unfavorable for the rapid permeability of electrolytic solution and freely comes in and goes out, thereby had a strong impact on the power characteristic of ultracapacitor, and made quite a few micropore can not get effective utilization.Need develop a kind of preparation method who had not only had high specific surface area but also the porous charcoal of enriching mesopore is arranged for this reason.
About the existing at present many reports of the preparation research of mesopore charcoal, its thinking mainly contains three directions:
(1) raw material direct activation method.As adopt steam activation, ZnCl
2Though activation waits gained mesopore proportion higher, its specific surface area is not high (mostly less than 1000m
2/ g).
(2) add pore-creating agent or catalyzer carbonization-activation again in organic precursor.The used method of patent of invention that is entitled as " method of making the mesopore charcoal " of people such as American Jia Dekaai and Tracy Hickman application is the charcoal precursor resole adding metal organic or inorganic compound at high charcoal productive rate, carry out charing, steam activation after a series of processing, the mesopore charcoal of gained has only lower specific surface area (450-800m
2/ g).
(3) on the porous molecular screen template, deposit organic raw material, after charing is handled, remove template again.Typical example such as Korean Wu Cheng mould etc. mix formation template/charcoal precursor composites with inorganic template (as silica) with the charcoal precursor, by obtaining charcoal/mould material after the charing processing, make the mesopore charcoal after removing template again.Though this mesopore charcoal can be controlled aperture and shape, its specific surface area is not high, and raw material subject range is narrow, technology is loaded down with trivial details, cost is higher.
Above-mentioned each class methods all are difficult to satisfy the desired active carbon with high specific surface area of ultracapacitor except the shortcoming of itself (such as cost height, raw material narrow application range or the like).
Summary of the invention
Purpose of the present invention just provides a kind of preparation method who had not only had high specific surface area but also had the porous charcoal of enriching mesopore.
It is to be raw material with each kind of plant body, hard coal, bituminous coal, brown coal, refinery coke, needle coke, charcoal fiber etc. for the present invention, after activated processing obtains gac, be raw material with the gac that obtains again, carry out re-activation with an amount of KOH, when its principle just is KOH and charcoal reaction, can be inserted in the aspect of C, make micropore, can obtain higher specific surface area like this thereby strut the charcoal layer.In addition, KOH also may penetrate in the existing micropore, by reaction the part micropore is subsided, thereby produces mesopore.Because it is very high once to activate gained porous charcoal porosity, do not produce so do not have a large amount of new holes during re-activation, the activator of this moment almost all is used for reaming.Therefore, obtaining porous charcoal had not only had high specific surface area, but also had had the mesopore of enriching.
The present invention prepares the method for mesopore charcoal, and its whole process of preparation is as follows:
(1) KOH is dissolved in water to dissolve (concentration is 500g-1000gKOH/L water) fully to KOH be 1～10: 1 the micropore charcoal to be immersed in the KOH solution by alkali charcoal mass ratio, at room temperature flooded 1-48 hour;
(2) the micropore charcoal speed with 2-20 ℃ in inert atmosphere after will flooding is raised to 600-900 ℃, then isothermal reaction 10-150min, naturally cooling afterwards;
(3) take out reactant, be washed with water to no OH
-Detect, be drying to obtain product.
Aforesaid micropore charcoal is to be raw material with the plant body, hard coal, bituminous coal, brown coal, refinery coke, needle coke or charcoal fiber etc., and activated processing obtains, though the specific surface area of this gac reaches 2700-3500m
2/ g, but the aperture, hole more than 85% is below 2nm.
And through after the re-activation reaming, though the porous charcoal specific surface area that obtains has decline in various degree, its mesopore significantly increases, and mesopore volume accounts for the about 65-85% of total pore volume.
The present invention has following advantage
1, KOH re-activation method raw material sources are abundant, and technology is simple, and is with low cost;
2, the porous charcoal mesopore that makes with this method is very abundant, and pore size distribution is narrow, the specific surface area height.
Embodiment
Embodiment 1
KOH is dissolved in water, and getting with the refinery coke than 5: 1 mass ratio with the alkali charcoal is that (specific surface area is 3024m for the gac of feedstock production
2, the micropore of aperture≤2nm account for total hole pore volume 86%) immerse in the KOH solution, at room temperature fully flood 18h.Then above-mentioned macerate is changed in the activation furnace and activate, temperature rise rate is 20 ℃/min, and at 900 ℃ of activation 0.5h down, reactivation process is led to protection of inert gas.The about 2700m of BET specific surface area of prepared gac
2, pore volume is 1.9cm
3/ g, mesopore volume account for 70% of total hole pore volume.
Embodiment 2
With the ground anthracite is that (specific surface area is 2840m to the prepared gac of raw material
2, the micropore of aperture≤2nm account for total hole pore volume 82%) with KOH with 1: 8 mass ratio batching, method is at room temperature flooded 6h with embodiment 1.Then above-mentioned macerate is changed in the activation furnace and activate, 10 ℃/min of temperature rise rate, at 800 ℃ of activation 1h down, reactivation process is led to protection of inert gas.The about 2580m of BET specific surface area of prepared gac
2, pore volume is 1.8cm
3/ g, mesopore volume account for 72% of total hole pore volume.
Embodiment 3
(specific surface area is 2680m with viscose base activated carbon fiber
2, the micropore of aperture≤2nm account for total hole pore volume 90%) for raw material, with the mass ratio batching of KOH with 1: 1, method is at room temperature flooded 48h with embodiment 1.Then above-mentioned macerate is changed in the activation furnace and activate, 2 ℃/min of temperature rise rate, at 600 ℃ of activation 1.5h down, reactivation process is led to protection of inert gas.The about 1880m of BET specific surface area of prepared activated carbon fiber
2, pore volume is 1.4cm
3/ g, mesopore volume account for 68% of total hole pore volume.
Embodiment 4
Nut-shell is that (specific surface area is 3105m for the gac of feedstock production
2, the micropore of aperture≤2nm account for total hole pore volume 92%) with KOH by 1: 6 mass ratio batching, method is at room temperature flooded 24h with embodiment 1.Then above-mentioned macerate is changed in the activation furnace and activate, 8 ℃/min of temperature rise rate, at 750 ℃ of activation 2.5h, reactivation process is led to protection of inert gas.The about 2760m of BET specific surface area of prepared gac
2, pore volume is 2.1cm
3/ g, mesopore volume account for 83% of total hole pore volume.
Embodiment 5
With needle coke (green coke) is that (specific surface area is 3496m for the gac of feedstock production
2, the micropore of aperture≤2nm account for total hole pore volume 89%) with KOH by 1: 1 mass ratio batching, method is at room temperature flooded 36h with embodiment 1.Then above-mentioned macerate is changed in the activation furnace and activate, 15 ℃/min of temperature rise rate, at 900 ℃ of activation 1h down, reactivation process is led to protection of inert gas.The about 3010m of BET specific surface area of prepared gac
2, pore volume is 2.4cm
3/ g, mesopore volume account for 65% of total hole pore volume.
Embodiment 6
With needle coke (green coke) is that (specific surface area is 3293m for the gac of feedstock production
2, the micropore of aperture≤2nm account for total hole pore volume 88%) with KOH by 1: 5 mass ratio batching, method is at room temperature flooded 24h with embodiment 1.Then above-mentioned macerate is changed in the activation furnace and activate, 5 ℃/min of temperature rise rate, at 800 ℃ of activation 1.5h down, reactivation process is led to protection of inert gas.The about 2800m of BET specific surface area of prepared gac
2, pore volume is 2.2cm
3/ g, mesopore volume account for 81% of total hole pore volume.
Embodiment 7
With needle coke (green coke) is that (specific surface area is 2751m for the gac of feedstock production
2, the micropore of aperture≤2nm account for total hole pore volume 81%) with KOH by 1: 10 mass ratio batching, method is at room temperature flooded 1h with embodiment 1.Then above-mentioned macerate is changed in the activation furnace and activate, 10 ℃/min of temperature rise rate, at 850 ℃ of activation 2h, reactivation process is led to protection of inert gas.The about 2350m of BET specific surface area of prepared gac
2, pore volume is 1.6cm
3/ g, mesopore volume account for 83% of total hole pore volume.
Claims (3)
1, a kind of preparation method of high-specific surface area mesopore charcoal, its feature is comprising the steps:
(1) KOH is dissolved in water to KOH and dissolves fully, its concentration is 500g-1000gKOH/L water, is 1～10: 1 the micropore charcoal to be immersed in the KOH solution by alkali charcoal mass ratio, at room temperature floods 1-48 hour;
(2) the micropore charcoal speed with 2-20 ℃ in inert atmosphere after will flooding is raised to 600-900 ℃, then isothermal reaction 10-150min, naturally cooling afterwards;
(3) take out reactant, be washed with water to no OH
-Detect, be drying to obtain product.
2, the preparation method of a kind of high-specific surface area mesopore charcoal as claimed in claim 1, its feature are to be raw material with the plant body, hard coal, bituminous coal, brown coal, refinery coke, needle coke or charcoal fiber at described micropore charcoal, and activated processing obtains.
3, the preparation method of a kind of high-specific surface area mesopore charcoal as claimed in claim 2, its feature is 2700-3500m in the specific surface area of described micropore charcoal
2/ g, the aperture in 85% above hole is below 2nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100123455A CN1304281C (en) | 2004-06-11 | 2004-06-11 | Preparing method for porous carbon with high specific surface area |
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|---|---|---|---|
| CNB2004100123455A CN1304281C (en) | 2004-06-11 | 2004-06-11 | Preparing method for porous carbon with high specific surface area |
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| CN1583550A true CN1583550A (en) | 2005-02-23 |
| CN1304281C CN1304281C (en) | 2007-03-14 |
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|---|---|---|---|---|
| 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 |
| CN101948106A (en) * | 2010-09-28 | 2011-01-19 | 华东理工大学 | Preparation method of blocky porous carbon with high specific surface area |
| CN101475168B (en) * | 2009-01-19 | 2011-04-20 | 中国科学院山西煤炭化学研究所 | Method for washing active carbon |
| CN102348638A (en) * | 2009-03-11 | 2012-02-08 | 英美烟草(投资)有限公司 | Methods for increasing mesopores into microporous carbon |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
| CN102515138A (en) * | 2011-11-09 | 2012-06-27 | 上海理工大学 | Preparation method of porous carbon with high specific surface area and in graded hole structure |
| 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 |
| CN103413690A (en) * | 2013-08-08 | 2013-11-27 | 方建辉 | Method for preparing mesoporous activated carbon used in supercapacitor by means of microwave modification |
| CN104785250A (en) * | 2015-03-13 | 2015-07-22 | 上虞盛晖化工股份有限公司 | Hydrogenation catalyst, its preparation method and its application in preparation of hexahydrophthalic anhydride |
| CN106423054A (en) * | 2016-09-19 | 2017-02-22 | 山西大同大学 | Process for preparing hot melt oil and mesoporous activated carbon simultaneously from low-rank coal |
| CN107055503A (en) * | 2017-02-28 | 2017-08-18 | 广西秀美壮乡能源环保有限公司 | A kind of preparation method of Mesoporous Carbon Materials |
| CN108862278A (en) * | 2018-05-29 | 2018-11-23 | 木林森活性炭江苏有限公司 | A kind of production method of drinks special-purpose activated charcoal |
| CN112216518A (en) * | 2020-09-15 | 2021-01-12 | 暨南大学 | Flexible zinc ion hybrid capacitor and preparation method and application thereof |
| CN113233462A (en) * | 2021-03-15 | 2021-08-10 | 河南省冶金研究所有限责任公司 | Preparation method of lignite-based activated carbon with high specific surface area |
| CN114300693A (en) * | 2021-12-30 | 2022-04-08 | 福州大学 | Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier |
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| CN1114481C (en) * | 2000-05-11 | 2003-07-16 | 中国科学院山西煤炭化学研究所 | Method for preparing active carbon for storing methane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101475168B (en) * | 2009-01-19 | 2011-04-20 | 中国科学院山西煤炭化学研究所 | Method for washing active carbon |
| CN102348638A (en) * | 2009-03-11 | 2012-02-08 | 英美烟草(投资)有限公司 | Methods for increasing mesopores into microporous carbon |
| CN101948106A (en) * | 2010-09-28 | 2011-01-19 | 华东理工大学 | Preparation method of blocky porous carbon with high specific surface area |
| CN101948106B (en) * | 2010-09-28 | 2013-03-27 | 华东理工大学 | Preparation method of blocky porous carbon with high specific surface area |
| CN102515138A (en) * | 2011-11-09 | 2012-06-27 | 上海理工大学 | Preparation method of porous carbon with high specific surface area and in graded hole structure |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
| 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 |
| CN103413690B (en) * | 2013-08-08 | 2016-08-10 | 福州多维炭环保技术有限公司 | A kind of method of the mesopore activated carbon using microwave modification to prepare ultracapacitor |
| CN103413690A (en) * | 2013-08-08 | 2013-11-27 | 方建辉 | Method for preparing mesoporous activated carbon used in supercapacitor by means of microwave modification |
| CN104785250A (en) * | 2015-03-13 | 2015-07-22 | 上虞盛晖化工股份有限公司 | Hydrogenation catalyst, its preparation method and its application in preparation of hexahydrophthalic anhydride |
| CN104785250B (en) * | 2015-03-13 | 2017-04-19 | 上虞盛晖化工股份有限公司 | Hydrogenation catalyst, its preparation method and its application in preparation of hexahydrophthalic anhydride |
| CN106423054A (en) * | 2016-09-19 | 2017-02-22 | 山西大同大学 | Process for preparing hot melt oil and mesoporous activated carbon simultaneously from low-rank coal |
| CN107055503A (en) * | 2017-02-28 | 2017-08-18 | 广西秀美壮乡能源环保有限公司 | A kind of preparation method of Mesoporous Carbon Materials |
| CN107055503B (en) * | 2017-02-28 | 2019-03-12 | 江苏丽鑫实业有限公司 | A kind of production method of Mesoporous Carbon Materials |
| CN108862278A (en) * | 2018-05-29 | 2018-11-23 | 木林森活性炭江苏有限公司 | A kind of production method of drinks special-purpose activated charcoal |
| CN112216518A (en) * | 2020-09-15 | 2021-01-12 | 暨南大学 | Flexible zinc ion hybrid capacitor and preparation method and application thereof |
| CN113233462A (en) * | 2021-03-15 | 2021-08-10 | 河南省冶金研究所有限责任公司 | Preparation method of lignite-based activated carbon with high specific surface area |
| CN114300693A (en) * | 2021-12-30 | 2022-04-08 | 福州大学 | Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier |
| CN114300693B (en) * | 2021-12-30 | 2024-03-12 | 福州大学 | Method for improving stability of fuel cell carbon-supported platinum-based catalyst by activating carbon carrier |
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| CN1304281C (en) | 2007-03-14 |
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Assignee: China Guodian Fuel Co., Ltd. Assignor: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2007.12.25 to 2015.12.25 Contract record no.: 2009990000653 Denomination of invention: Preparing method for porous carbon with high specific surface area Granted publication date: 20070314 License type: Exclusive license Record date: 20090612 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.12.25 TO 2015.12.25; CHANGE OF CONTRACT Name of requester: GUODIAN FUEL CO., LTD. Effective date: 20090612 |
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