CN102491320B - Pitch-based active carbon with superhigh specific surface area and preparation method thereof - Google Patents
Pitch-based active carbon with superhigh specific surface area and preparation method thereof Download PDFInfo
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- CN102491320B CN102491320B CN2011103823399A CN201110382339A CN102491320B CN 102491320 B CN102491320 B CN 102491320B CN 2011103823399 A CN2011103823399 A CN 2011103823399A CN 201110382339 A CN201110382339 A CN 201110382339A CN 102491320 B CN102491320 B CN 102491320B
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Abstract
The invention discloses a pitch-based active carbon with superhigh specific surface area and a preparation method thereof. The pitch-based active carbon with superhigh specific surface area is prepared by using pitch and rosin as raw materials, and carrying out concocting, pyrolysis, pre-oxidation and activation. Compared with routine methods for preparing active carbon with superhigh specific surface area, the method has the advantages of low preparation cost, low device investment, simple operation, no pollution, and easy realization of industrialization, and the prepared pitch-based active carbon has the advantages of large specific surface area, good performance, and good physical and chemical stability, and has outstanding economic and social benefits.
Description
Technical field
The invention belongs to the Carbon Materials field, be specifically related to a kind of pitch-based active carbon with superhigh specific surface area and preparation method thereof.
Background technology
Gac is a kind of porous carbon material that pore texture is flourishing, specific surface area is large that is made of crystallite charcoal and unformed charcoal.Gac has good absorption property and the good excellent properties such as chemical stability, physical stability and good regenerative power, and it has been widely used in the fields such as electronics, chemical industry, food-processing, health care, transportation and energy, agricultural, national defence as sorbent material, support of the catalyst etc.Yet along with the development in the fields such as medicine, environmental protection, military affairs, common gac (specific surface area 800～1500m
2/ g) relatively poor due to Selective adsorption, specific surface area is low, loading capacity is limited, can not satisfy the particular requirement in these fields, this makes the demand to active carbon with high specific surface area constantly rise.(specific surface area is generally greater than 2500m for activated carbon with high specific surface area
2/ g) have the advantages such as specific surface area is high, microvoid content is high, pore size distribution is narrow, adsorptive capacity is large, can be used for double layer capacitor, natural gas storage, reclaim the fields such as enriching noble metals, methane adsorbent, effective catalyst and support of the catalyst.
The preparation method of activated carbon with high specific surface area has physical activation method, chemical activation method and the chemical combined activation method of Wu Li –.It is raw material that the preparation activated carbon with high specific surface area often adopts refinery coke, coal-tar pitch, mesophase pitch and MCMB, the above two are due to the restriction of raw material mix and aspect of performance, be difficult to prepare activated carbon with high specific surface area, then both preparation costs are too high, the suitable feedstock that neither prepare activated carbon with high specific surface area, this has directly affected the propagation and employment of activated carbon with high specific surface area.
Summary of the invention
The object of the invention is to a kind of pitch-based active carbon with superhigh specific surface area and preparation method thereof, prepare activated carbon with high specific surface area relatively with routine, the present invention has that preparation cost is low, equipment investment is few, and is simple to operate, pollution-free, easily realizes industrialization; The advantage that the product specific surface area is large, functional, physical and chemical stability is good possesses significant economic and social benefit.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of pitch-based active carbon with superhigh specific surface area comprises modulation, pyrolytic reaction, preoxidation and the activating process of raw material.Its concrete steps are as follows:
(1) modulation of raw material:
Basic raw material: one or more mixtures of coal-tar pitch, petroleum pitch, slag oil asphalt, synthetic asphalts;
Additive: one or both of rosin, nilox resin;
Proportioning raw materials: the mass ratio of basic raw material and additive is 100:5-100:30;
Basic raw material and additive take by proportioning, grind after 80 mesh sieves and directly mix, and put into polymeric kettle, are warming up to the technique that adopts hot melt to stir after preset temperature and mix, and processing parameter is:
Temperature rise rate: 50 ℃/min of 2 ℃/min –;
Preset temperature: 100 200 ℃ of ℃ –;
Churning time: 0.1h – 1h;
Stirring velocity: 50 rpm – 1000 rpm;
Protective atmosphere: N
2Perhaps Ar
2
Gas flow: 50 mL/min – 200 mL/min;
(2) pyrolytic reaction:
The raw material that step (1) modulates is put into atmosphere furnace, be incubated after then being warming up to preset temperature, be cooled to room temperature and take out, processing parameter is:
Temperature rise rate: 100 ℃/min of 2 ℃/min –;
Preset temperature: 400 500 ℃ of ℃ –;
Soaking time: 0.5h – 3h;
Protective atmosphere: N
2Perhaps Ar
2
Gas flow: 50 mL/min – 200 mL/min;
(3) preoxidation
Put into reactor after the resulting product grinding of step (2) is sieved, then warming while stirring is incubated to preset temperature, passes into air simultaneously in whipping process, is cooled to room temperature and takes out, and processing parameter is:
The resulting product mesh-of-grind of step (2): 60-300 order;
Temperature rise rate: 100 ℃/min of 2 ℃/min –;
Preset temperature: 240 350 ℃ of ℃ –;
Soaking time: 0 – 10h;
Gas flow: 100mL/min – 250mL/min;
(4) activating process
The resulting product of step (3) and KOH are mixed put into corundum crucible, be incubated after then being warming up to preset temperature in High Temperature Furnaces Heating Apparatus, cool to room temperature with the furnace and take out, washing is drying to obtain described pitch-based active carbon with superhigh specific surface area; Processing parameter is:
Proportioning raw materials: the mass ratio of the resulting product of step (3) and KOH is 1:3-1:9;
Temperature rise rate: 10 ℃/min of 2 ℃/min –;
Preset temperature: 700 900 ℃ of ℃ –;
Soaking time: 0.15h – 2 h;
Protective atmosphere: N
2Perhaps Ar
2
Gas flow: 50 mL/min – 200 mL/min.
The present invention reaches the purpose of adjusting pitch-based active carbon with superhigh specific surface area structure and performance by modulation, pyrolysis, preoxidation and the activating process of controlling basic raw material.The specific surface area that adopts the prepared gac of preparation method of the present invention is 2500 ~ 3500m
2/ g.
The present invention modulates modification by adding a certain amount of rosin to material asphalt, is used for preparing activated carbon with high specific surface area through the alternative mesophase pitch of pyrolytic reaction products therefrom or MCMB.The activated carbon with high specific surface area of Using such method preparation has advantages of that cost is low, technique simple, excellent property, pollution-free, easy industrialization.
Compared with prior art, the advantage and the effect that have of the present invention is:
(1) abundant raw material, cheap.
(2) processing unit is simple, and is pollution-free, is easy to scale operation.
(3) specific surface area is high, and is of many uses.
Embodiment
Be below several specific embodiment of the present invention, further illustrate the present invention, but the present invention be not limited only to this.
Embodiment 1
Coal-tar pitch and nilox resin are ground to 80 orders, the polymeric kettle of packing into after 100:10 mixes in mass ratio, the speed intensification with 3 ℃/min is warming up to 150 ℃, and begins to pass into N from intensification
2, N
2Flow is 50mL/min, simultaneously rotating speed is transferred to 500rpm and stirs 0.1h, namely obtains the pitch that modulates.The pitch that modulates is put into atmosphere furnace (N
2Flow is 50mL/min), be incubated 2h after then being warming up to 450 ℃ with 5 ℃/min, be cooled to room temperature and take out pyrolysis product.Put into reactor after pyrolysis product is ground to 300 orders, then under agitation and with the heat-up rate of 4 ℃/min rise to 300 ℃ of reaction 1 h, pass into air with 200mL/min in reaction process, reaction is cooled to room temperature after finishing.With the product after oxidation and KOH in mass ratio 1:5 mix and put into reactor, and pass into N
2, N
2Flow is 50mL/min, keeps 1 h after then being warming up to 850 ℃ with 5 ℃/min, cools to room temperature with the furnace and takes out, and is washed to neutrality, and drying namely obtains gac.Prepared gac has following performance: specific surface area 3320m
2/ g, total hole volume 1.97cm
3/ g, benzene adsorptive value 1560mg/g.
Embodiment 2
With petroleum pitch and rosin by the 100:5(mass ratio) take, be ground to the polymeric kettle of packing into after 80 orders, heat up with the speed of 10 ℃/min, be warming up to 120 ℃, and begin to pass into N from intensification
2, N
2Flow is 100mL/min, simultaneously rotating speed is transferred to 200rpm and stirs 0.5h, namely obtains the pitch that modulates.The pitch that modulates is put into atmosphere furnace (N
2Flow is 100 mL/min), be incubated 2.5h after then being warming up to 400 ℃ with 5 ℃/min, be cooled to room temperature and take out pyrolysis product.Put into reactor after pyrolysis product is ground to 60 orders, then under agitation and with the heat-up rate of 25 ℃/min rise to 260 ℃ of reaction 3 h, pass into air with 160 mL/min in reaction process, reaction is cooled to room temperature after finishing.With the product after oxidation and KOH in mass ratio 1:7 mix and put into reactor, and pass into N
2, N
2Flow is 50mL/min, keeps 2 h after then being warming up to 900 ℃ with 10 ℃/min, cools to room temperature with the furnace and takes out, and is washed to neutrality, and drying namely obtains gac.Prepared gac has following performance: specific surface area 2800m
2/ g, total hole volume 1.79cm
3/ g, benzene adsorptive value 1437mg/g.
Embodiment 3
With matchmaker's pitch and rosin by the 100:15(mass ratio) take, be ground to the polymeric kettle of packing into after 80 orders, heat up with the speed of 5 ℃/min, be warming up to 180 ℃, and begin to pass into N from intensification
2, N
2Flow is 100mL/min, simultaneously rotating speed is transferred to 800rpm and stirs 0.4h, namely obtains the pitch that modulates.The pitch that modulates is put into atmosphere furnace (N
2Flow is 100 mL/min), be incubated 2.5h after then being warming up to 480 ℃ with 10 ℃/min, be cooled to room temperature and take out pyrolysis product.Put into reactor after pyrolysis product is ground to 200 orders, then under agitation rise to 240 ℃ of reaction 10 h with the heat-up rate of 10 ℃/min, pass into air with 150 mL/min in reaction process, reaction is cooled to room temperature after finishing.With the product after oxidation and KOH in mass ratio 1:9 mix and put into reactor, and pass into N
2, N
2Flow is 50mL/min, keeps 5h after then being warming up to 700 ℃ with 5 ℃/min, cools to room temperature with the furnace and takes out, and is washed to neutrality, and drying namely obtains gac.Prepared gac has following performance: specific surface area 3000m
2/ g, total hole volume 1.76cm
3/ g, benzene adsorptive value 1457mg/g.
Embodiment 4
With synthetic asphalts and rosin by the 100:20(mass ratio) take, be ground to the polymeric kettle of packing into after 80 orders, heat up with the speed of 25 ℃/min, be warming up to 200 ℃, and begin to pass into N from intensification
2, N
2Flow is 140mL/min, simultaneously rotating speed is transferred to 500rpm and stirs 1h, namely obtains the pitch that modulates.The pitch that modulates is put into atmosphere furnace (N
2Flow is 150 mL/min), be incubated 2h after then being warming up to 500 ℃ with 5 ℃/min, be cooled to room temperature and take out pyrolysis product.Put into reactor after pyrolysis product is ground to 100 orders, then under agitation rise to 280 ℃ of reaction 3 h with the heat-up rate of 25 ℃/min, pass into air with 250 mL/min in reaction process, reaction is cooled to room temperature after finishing.With the product after oxidation and KOH in mass ratio 1:3 mix and put into reactor, and pass into N
2, N
2Flow is 50mL/min, keeps 2 h after then being warming up to 800 ℃ with 8 ℃/min, cools to room temperature with the furnace and takes out, and is washed to neutrality, and drying namely obtains gac.Prepared gac has following performance: specific surface area 2580m
2/ g, total hole volume 1.32m
3/ g, benzene adsorptive value 1243mg/g.
Embodiment 5
With petroleum pitch and coal-tar pitch in mass ratio 1:3 mix.With mix asphalt and nilox resin by the 100:20(mass ratio) take, be ground to the polymeric kettle of packing into after 80 orders, heat up with the speed of 3 ℃/min, be warming up to 150 ℃, and begin to pass into N from intensification
2, N
2Flow is 50mL/min, simultaneously rotating speed is transferred to 200rpm and stirs 1h, namely obtains the pitch that modulates.The pitch that modulates is put into atmosphere furnace (N
2Flow is 50 mL/min), be incubated 2h after then being warming up to 500 ℃ with 5 ℃/min, be cooled to room temperature and take out pyrolysis product.Put into reactor after pyrolysis product is ground to 200 orders, then under agitation rise to 300 ℃ of reaction 2 h with the heat-up rate of 100 ℃/min, pass into air with 100mL/min in reaction process, reaction is cooled to room temperature after finishing.With the product after oxidation and KOH in mass ratio 1:5 mix and put into reactor, and pass into N
2, N
2Flow is 50mL/min, keeps 1.5h after then being warming up to 850 ℃ with 5 ℃/min, cools to room temperature with the furnace and takes out, and is washed to neutrality, and drying namely obtains gac.Prepared gac has following performance: specific surface area 2930m
2/ g, total hole volume 1.82m
3/ g, benzene adsorptive value 1457mg/g.
Embodiment 6
With synthetic asphalts and coal-tar pitch in mass ratio 1:1 mix.With mix asphalt and rosin by the 100:30(weight ratio) take, be ground to the polymeric kettle of packing into after 80 orders, heat up with the speed of 2 ℃/min, be warming up to 160 ℃, and begin to pass into N from intensification
2, N
2Flow is 200mL/min, simultaneously rotating speed is transferred to 300rpm and stirs 0.5h, namely obtains the pitch that modulates.The pitch that modulates is put into atmosphere furnace (N
2Flow is 50 mL/min), be incubated 2h after then being warming up to 500 ℃ with 15 ℃/min, be cooled to room temperature and take out pyrolysis product.Put into reactor after pyrolysis product is ground to 100 orders, then under agitation rise to 320 ℃ of reaction 2h with the heat-up rate of 20 ℃/min, pass into air with 200mL/min in reaction process, reaction is cooled to room temperature after finishing.With the product after oxidation and KOH in mass ratio 1:4 mix and put into reactor, and pass into N
2, N
2Flow is 50mL/min, keeps 0.5h after then being warming up to 900 ℃ with 10 ℃/min, cools to room temperature with the furnace and takes out, and is washed to neutrality, and drying namely obtains gac.Prepared gac has following performance: specific surface area 2740m
2/ g, total hole volume 1.52m
3/ g, benzene adsorptive value 1321mg/g.
The above is only preferred embodiment of the present invention, and all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1. the preparation method of a pitch-based active carbon with superhigh specific surface area, it is characterized in that: the specific surface area of described asphalt based active carbon is 2500-3500m
2/ g;
The preparation method comprises modulation, pyrolytic reaction, preoxidation and the activating process of raw material;
Concrete steps are as follows:
(1) modulation of raw material:
Basic raw material: one or more mixtures of coal-tar pitch, petroleum pitch, slag oil asphalt, synthetic asphalts;
Additive: one or both of rosin, nilox resin;
Proportioning raw materials: the mass ratio of basic raw material and additive is 100:5-100:30;
Basic raw material and additive take by proportioning, grind after 80 mesh sieves and directly mix, and put into polymeric kettle, are warming up to the technique that adopts hot melt to stir after preset temperature and mix, and processing parameter is:
Temperature rise rate: 50 ℃/min of 2 ℃/min –;
Preset temperature: 100 200 ℃ of ℃ –;
Churning time: 0.1h – 1h;
Stirring velocity: 50 rpm – 1000 rpm;
Protective atmosphere: N
2Perhaps Ar;
Gas flow: 50 mL/min – 200 mL/min;
(2) pyrolytic reaction:
The raw material that step (1) modulates is put into atmosphere furnace, be incubated after then being warming up to preset temperature, be cooled to room temperature and take out, processing parameter is:
Temperature rise rate: 100 ℃/min of 2 ℃/min –;
Preset temperature: 400 500 ℃ of ℃ –;
Soaking time: 0.5h – 3h;
Protective atmosphere: N
2Perhaps Ar;
Gas flow: 50 mL/min – 200 mL/min;
(3) preoxidation
Put into reactor after the resulting product grinding of step (2) is sieved, then warming while stirring is incubated to preset temperature, passes into air simultaneously in whipping process, is cooled to room temperature and takes out, and processing parameter is:
The resulting product mesh-of-grind of step (2): 60-300 order;
Temperature rise rate: 100 ℃/min of 2 ℃/min –;
Preset temperature: 240 350 ℃ of ℃ –;
Soaking time: 0 – 10h;
Gas flow: 100mL/min – 250mL/min;
(4) activating process
The resulting product of step (3) and KOH are mixed put into corundum crucible, be incubated after then being warming up to preset temperature in High Temperature Furnaces Heating Apparatus, cool to room temperature with the furnace and take out, washing is drying to obtain described pitch-based active carbon with superhigh specific surface area; Processing parameter is:
Proportioning raw materials: the mass ratio of the resulting product of step (3) and KOH is 1:3-1:9;
Temperature rise rate: 10 ℃/min of 2 ℃/min –;
Preset temperature: 700 900 ℃ of ℃ –;
Soaking time: 0.15h – 2 h;
Protective atmosphere: N
2Perhaps Ar;
Gas flow: 50 mL/min – 200 mL/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521194A (en) * | 2013-08-30 | 2014-01-22 | 蚌埠德美过滤技术有限公司 | Surface polymer modified wood charcoal adsorbing agent and preparation method thereof |
| CN103613096B (en) * | 2013-12-06 | 2015-03-04 | 福州大学 | Low-cost method for preparing graphene macroform |
| CN103803550B (en) * | 2014-02-26 | 2016-05-18 | 北京宝塔三聚能源科技有限公司 | A kind of preparation method of asphalt based active carbon |
| CN105148827A (en) * | 2015-10-13 | 2015-12-16 | 中国石油化工股份有限公司 | Method for preparing absorbing agent for chemical leakage accident by adopting waste catalytic cracking catalyst |
| CN106732416B (en) * | 2016-12-01 | 2019-04-12 | 桂林理工大学 | A kind of preparation method and applications of rosin modification stalk adsorbent |
| CN107601500A (en) * | 2017-11-02 | 2018-01-19 | 福州大学 | A kind of preparation method of high-specific surface area active foam Carbon Materials |
| CN108010750B (en) * | 2017-12-29 | 2019-08-09 | 福州大学 | A kind of preparation method of ultra-thin-wall multistage porous charcoal/carbon/polyaniline super capacitor electrode material |
| CN108940134B (en) * | 2018-06-20 | 2020-07-31 | 东南大学 | Continuous reaction device and method for coal tar pitch ball oxidation infusibility |
| CN109399635A (en) * | 2018-09-29 | 2019-03-01 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of the asphaltic base honeycomb hole nanometer layer of charcoal suitable for electrochemical applications |
| CN110465267B (en) * | 2019-07-08 | 2022-08-19 | 天津大学 | Method for preparing nitrogen-sulfur-rich porous adsorbent material from oil sand asphaltene and application |
| CN111762779B (en) * | 2020-07-20 | 2021-08-13 | 广东东煌科技有限公司 | Coal-based activated carbon, columnar activated carbon and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927709A (en) * | 2006-09-12 | 2007-03-14 | 山西大学 | Asphalt based active carbon and preparation method thereof |
| CN101717085A (en) * | 2009-12-07 | 2010-06-02 | 北京化工大学 | Activated carbon microspheres and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927709A (en) * | 2006-09-12 | 2007-03-14 | 山西大学 | Asphalt based active carbon and preparation method thereof |
| CN101717085A (en) * | 2009-12-07 | 2010-06-02 | 北京化工大学 | Activated carbon microspheres and preparation method thereof |
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