CN104803381B - Hunan oil-tea camellia husks is utilized to prepare method and this activated carbon and the application thereof of activated carbon - Google Patents
Hunan oil-tea camellia husks is utilized to prepare method and this activated carbon and the application thereof of activated carbon Download PDFInfo
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- CN104803381B CN104803381B CN201510132681.1A CN201510132681A CN104803381B CN 104803381 B CN104803381 B CN 104803381B CN 201510132681 A CN201510132681 A CN 201510132681A CN 104803381 B CN104803381 B CN 104803381B
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Abstract
The present invention relates to a kind of method utilizing Hunan oil-tea camellia husks to prepare activated carbon and this activated carbon and application thereof, belong to biological chemical field.The method comprises the following steps: Hunan oil-tea camellia husks is dried, crushes, is sieved；With aqueous slkali, Hunan oil-tea camellia husks powder is impregnated again；Once being activated by Hunan oil-tea camellia husks powder microwave after dipping, the temperature once activated is 200 ~ 450 DEG C, the time is 0.5 ~ 2h；By the Hunan oil-tea camellia husks burgy after once activation, it is grinding to obtain powdered carbon；Adding strong acid solution, heated by microwave ash disposal in described powdered carbon, the temperature of ash disposal is 200 ~ 450 DEG C, the time is 0.5 ~ 1h, after ash disposal with water by powdered carbon washing to neutral；Adding the water of 1 ~ 5 times of quality in powdered carbon after washing, carrying out re-activation with microwave until being dried, obtaining activated carbon, the temperature of re-activation is 200 ~ 450 DEG C.Activated carbon prepared by the method is be applicable to ultracapacitor.
Description
Technical field
The present invention relates to a kind of method utilizing Hunan oil-tea camellia husks to prepare activated carbon and this activated carbon and application thereof, belong to biological chemical field.
Background technology
The energy, environmental problem are the major issues that the whole world faces, and in the trend being on the rise, force various countries to strive to find new forms of energy and new energy conversion and storing mode.Ultracapacitor is as the storage of energy and transform mode, because of advantages such as charge rate is fast, power big, life-span length, it is widely used in electronic product (coordinating machine, computer memory), also begins to be applied to electric automobile, crane, subway homenergic supplement and recovery etc..Activated carbon is the electrode material that ultracapacitor uses the earliest, is also the sole carbon material of current commercialization double layer capacitor.The performance of activated carbon and price become restriction ultracapacitor development and the key factor of application.
The source of activated carbon mainly has three kinds, including activated carbon from activated sludge (shell, trees etc.), coal mass active carbon, resin activity charcoal.The quality of coal mass active carbon is affected by ature of coal amount, and particularly resource-constrained, non-renewable characteristic constrains its development.Resin activity charcoal stable performance, but resin making technique is complicated, expensive.Prepare activated carbon with biomass as raw material, there is aboundresources, reproducible a little meet the needs of low-carbon (LC) social development, be increasingly becoming the focus of people's research and development.Particularly shell is as the side-product of agricultural, and resource is the abundantest, itself has abundant natural void structure, is the quality raw materials being prepared as activated carbon.But there is acid or the problem such as alkali consumption is big in the existing patented technology preparing super capacitor active carbon, acid at concentrations up to 72% when preparing super capacitor active carbon such as Chinese patent (CN 102205963 A), alkali charcoal mass ratio when Chinese patent (CN 103539114 A) prepares super capacitor active carbon is up to 5:1), the most a high proportion of acid, alkaloid substance, not only corrosivity is strong, easily cause environmental pollution but also to directly result in production cost higher.At present, coconut husk, Pericarppium Armeniacae Amarum etc. are used as the main source of ultracapacitor activated carbon, but these materials are affected by climate reasons in China, and resource distribution region is strong, limited source.
Oil-tea camellia husks is the by-product after Semen Camelliae separation kernel.Oil tea is that China has distinctive woody oleiferous plants crop, is mainly distributed on Hunan, Hubei, Guangdong, Guangxi, Fujian, Jiangxi etc. and saves.The Hunan oil-tea camellia husks i.e. place of production is the oil-tea camellia husks in Hunan.China's existing oil tea area about 400 × 104 hm2, produce camellia oleifera fruit nearly 560 × 10 per year4t.In recent years, country carries forward vigorously the development of camellia oleiferaindustry, and tea-oil tree yield grows steadily year by year.Hunan oil-tea camellia husks accounts for the 60% of camellia oleifera fruit weight, and resource is the abundantest.Hunan oil-tea camellia husks major part is scattered in peasant's hands at present, acts substantially as the fuel warmed oneself by a fire winter and uses, and added value is low, pollute environment.
Hunan oil-tea camellia husks is mainly made up of lignin, cellulose etc., is the quality raw materials preparing activated carbon.Along with the reinforcement that the utilization of resources is realized, people start with Hunan oil-tea camellia husks prepare absorption activated carbon (a. Li Jiaxing etc., processing of farm products (academic periodical), 2013,10:20-24；B. horsepower etc., grain and food industry, 2009,16 (3): 19-21；C. Long Liujin etc., Guangxi University's journal: natural science edition, 2012,37 (3): 425-429), but the quality of prepared activated carbon is the highest, only can be used as industrial adsorbents and uses.Chinese patent (CN 102502628 A, CN 103011155 A) all uses high-concentration phosphoric acid (80%) to process the Hunan oil-tea camellia husks preparation activated carbon for absorption；Chinese patent (CN 103030710 A) then uses high concentration zinc chloride (50%) or high-alkali charcoal ratio (4:1) to process the Hunan oil-tea camellia husks preparation activated carbon for absorption.These technology use the acid of high concentration or high alkali charcoal ratio, belong to traditional active charcoal preparing process, there is the problems such as cost is high, environmental pollution is serious, product quality is the highest.
Summary of the invention
Present invention solves the technical problem that and be, be reduced by Hunan oil-tea camellia husks and prepare the production cost of activated carbon, improve the product quality of activated carbon.
The technical scheme is that, it is provided that a kind of method utilizing Hunan oil-tea camellia husks to prepare activated carbon, comprise the following steps:
(1) Hunan oil-tea camellia husks is dried, crushes, sieves, obtain Hunan oil-tea camellia husks powder；
(2) with aqueous slkali, described Hunan oil-tea camellia husks powder is impregnated again；
(3) once being activated by the Hunan oil-tea camellia husks powder microwave after dipping, the temperature once activated is 200 ~ 450 DEG C, the time is 0.5 ~ 2h；
(4) by the Hunan oil-tea camellia husks burgy after once activation, it is grinding to obtain powdered carbon；
(5) adding strong acid solution, heated by microwave ash disposal in described powdered carbon, the temperature of ash disposal is 200 ~ 450 DEG C, the time is 0.5 ~ 1h, after ash disposal with water by powdered carbon washing to neutral；
(6) adding the water of 1 ~ 5 times of quality in powdered carbon after washing, carrying out re-activation with microwave until being dried, obtaining activated carbon, the temperature of re-activation is 200 ~ 450 DEG C.
Further, described aqueous slkali is NaOH or the KOH solution of 2 ~ 5wt%.
Further, described dipping temperature be 70 ~ 90 DEG C, the time be 7 ~ 24h.
Further, in described step (1), the particle diameter of Hunan oil-tea camellia husks powder is 20 ~ 100 mesh.
Further, the particle diameter of described powdered carbon is 4 ~ 8 m.
Further, described strong acid solution is HCl or H of 0.5 ~ 5wt%2SO4Solution.
Further, the temperature of described carbonization be 700 ~ 900 DEG C, the time be 0.5 ~ 2h.
The present invention further provides and make in aforementioned manners, utilize Hunan oil-tea camellia husks to produce activated carbon.
Further, the aperture of described activated carbon is 3 ~ 4nm.
The present invention also provides for the application in ultracapacitor of the above-mentioned activated carbon.
The present invention utilizes resourceful shell of Camelliaoleifera Abel for raw material, activates the technology such as reaming and second reaming with low concentration diluted alkaline pretreatment raw material, microwave-assisted, it is achieved that the preparation of high-quality ultracapacitor activated carbon.
The principle of microwave heating is that polar substances molecule absorbs electromagnetic energy in microwave electromagnetic field, produces heat energy with hypervelocity vibration.Therefore, microwave heating has feature uniform, quick.The present invention utilizes microwave heating pretreatment Hunan oil-tea camellia husks, be conducive to driving alkali (such as NaOH/KOH) internal to its biological tissue cell and micropore spreads, increase the activity of the composition such as lignin degrading, cellulose and reaction rate, thus reduce the concentration of alkali, shortening processes the time and i.e. can reach the purpose producing activated carbon；And then be conducive to protection production equipment, reduce production cost and protection environment.
Utilize microwave heating ash disposal, when activating and be dried, owing to being three-dimensional mode of heating simultaneously from inside to outside to adding hot object, simultaneously drive hydrone inside hole, the particularly aperture diffusion motion repeatedly of micropore (diameter is less than 2nm) carries out re-activation reaming, and beneficially through between multi-stage porous, substantially increase the ratio of mesopore, reach ultracapacitor requirement rational to absorbent charcoal material pore-size distribution, and then add the electro-chemical activity of ultracapacitor.Wherein, ash disposal refers to the process of non-carbon Impurity removal in activated carbon, mainly for removing the metallics in activated carbon.
The temperature and time of microwave heating is the most important parameter in aperture controlling activated carbon, if the temperature of microwave heating is too high or heat time heating time is long, the aperture of activated carbon can be caused to grow up, and excessive aperture can affect the performance of activated carbon.
The invention has the beneficial effects as follows, in conjunction with microwave activation, ash cleaning technology, using the aqueous slkali of low concentration can realize utilizing Hunan oil-tea camellia husks to prepare activated carbon, this Properties of Activated Carbon is excellent, and mesopore proportion is high, higher than electric capacity, can be used in ultracapacitor.
Detailed description of the invention
Embodiment
1
The method utilizing Hunan oil-tea camellia husks to prepare activated carbon that the present embodiment provides comprises the following steps:
A. Hunan oil-tea camellia husks is dried at a temperature of 250 DEG C, be crushed to certain particle size, cross 20 mesh sieves standby.
B. being 1:4 dipping by Hunan oil-tea camellia husks powder and the 2%KOH mass ratio of crossing 20 mesh, temperature is 70 DEG C, and the time is 24h.
C. once being activated by the Hunan oil-tea camellia husks powder microwave impregnated, the temperature once activated is 200 DEG C, and the time is 2h.
D. by the Hunan oil-tea camellia husks powder retort carbonization after once activation, temperature is 700 DEG C, and the time is 2h；Pulverize through twin rollers again, then pulverize further with ball mill, obtain the powdered carbon that particle size range is 4 ~ 7 m.
The most above-mentioned powdered carbon concentration is 0.5% hydrochloric acid heated by microwave ash disposal, and temperature is 450 DEG C, and the time is 0.5h, then filters and with high purity water washing to neutral.
F. adding and the ultra-pure water of the quality such as powdered carbon, by microwave heating temperature to 450 DEG C, the time is that 0.5h carries out re-activation, until being dried, obtains activated carbon product.
After testing, this activated carbon specific surface area is 1268m2/ g, iodine sorption value 560.60mg/g, methylene blue adsorption value 450.58mg/g, density is 0.45g/mL, and average pore size is 3.8nm, pH=6, and the ratio electric capacity of capacitor is 268F/g.
Embodiment
2
The method utilizing Hunan oil-tea camellia husks to prepare activated carbon that the present embodiment provides comprises the following steps:
A. Hunan oil-tea camellia husks is dried at a temperature of 250 DEG C, be crushed to certain particle size, cross 50 mesh sieves standby.
B. being 1:1 dipping by the Hunan oil-tea camellia husks powder of 50 mesh and 3%KOH mass ratio, temperature is 90 DEG C, and the time is 7h.
C. once being activated by the Hunan oil-tea camellia husks powder microwave impregnated, the temperature once activated is 450 DEG C, and the time is 0.5h.
D. by the Hunan oil-tea camellia husks powder retort carbonization after once activation, temperature is 900 DEG C, and the time is 0.5h；Pulverize through twin rollers again, then pulverize further with ball mill, obtain the powdered carbon that particle size range is 4 ~ 8 m.
The most above-mentioned powdered carbon concentration is 2% hydrochloric acid heated by microwave ash disposal, and temperature is 200 DEG C, and the time is 1h, then filters and with high purity water washing to neutral.
F. adding the ultra-pure water of 3 times of powdered carbon quality, carry out re-activation with microwave heating, microwave heating temperature is 450 DEG C, and activation, until being dried, obtains activated carbon product..
After testing, this activated carbon specific surface area is 1310m2/ g, iodine sorption value 479.60mg/g, methylene blue adsorption value 419.70mg/g, density is 0.42g/ml, and average pore size is 3.3nm, pH=8, and the ratio electric capacity of capacitor is 256F/g.
Embodiment
3
The method utilizing Hunan oil-tea camellia husks to prepare activated carbon that the present embodiment provides comprises the following steps:
A. Hunan oil-tea camellia husks is dried at a temperature of 250 DEG C, be crushed to certain particle size, cross 100 mesh sieves standby.
B. being 1:2 dipping by the Hunan oil-tea camellia husks powder of 100 mesh and 5%KOH mass ratio, temperature is 80 DEG C, and the time is 18h.
C. once being activated by the Hunan oil-tea camellia husks powder microwave impregnated, the temperature once activated is 200 DEG C, and the time is 1h.
D. by the raw material retort carbonization after once activation, temperature is 700 DEG C, and the time is 1.5h；Pulverize through twin rollers again, then pulverize further with ball mill, obtain the powdered carbon that particle size range is 4 ~ 7 m.
The most above-mentioned powdered carbon concentration is 0.5% hydrochloric acid heated by microwave ash disposal, and temperature is 450 DEG C, and the time is 1h, then filters and with high purity water washing to neutral.
F. adding the ultra-pure water of 2 times of powdered carbon quality, by microwave heating temperature to 300 DEG C, carry out re-activation, continuing with microwave heating, until being dried, to obtain activated carbon product.
After testing, this activated carbon specific surface area is 1258m2/ g, iodine sorption value 529.60mg/g, methylene blue adsorption value 453.58mg/g, density is 0.45g/ml, and average pore size is 3.2nm, pH=6, and the electric capacity of capacitor is 232F/g.
Claims (9)
1. one kind utilizes the method that Hunan oil-tea camellia husks prepares activated carbon, it is characterised in that comprise the following steps:
(1) Hunan oil-tea camellia husks is dried, crushes, sieves, obtain Hunan oil-tea camellia husks powder；
(2) being impregnated by described Hunan oil-tea camellia husks powder with aqueous slkali, described aqueous slkali is NaOH or the KOH solution of 2 ~ 5wt% again；
(3) once being activated by the Hunan oil-tea camellia husks powder microwave after dipping, the temperature once activated is 200 ~ 450 DEG C, the time is 0.5 ~ 2h；
(4) by the Hunan oil-tea camellia husks burgy after once activation, it is grinding to obtain powdered carbon；
(5) adding strong acid solution, heated by microwave ash disposal in described powdered carbon, the temperature of ash disposal is 200 ~ 450 DEG C, the time is 0.5 ~ 1h, after ash disposal with water by powdered carbon washing to neutral；
(6) adding the water of 1 ~ 5 times of quality in powdered carbon after washing, carrying out re-activation with microwave until being dried, obtaining activated carbon, the temperature of re-activation is 200 ~ 450 DEG C.
2. the method for claim 1, it is characterised in that described dipping temperature is 70 ~ 90 DEG C, the time is 7 ~ 24h.
3. the method for claim 1, it is characterised in that in described step (1), the particle diameter of Hunan oil-tea camellia husks powder is 20 ~ 100 mesh.
4. the method for claim 1, it is characterised in that the particle diameter of described powdered carbon is 4 ~ 8 m.
5. the method for claim 1, it is characterised in that described strong acid solution is HCl or H of 0.5 ~ 5wt%2SO4Solution.
6. the method for claim 1, it is characterised in that the temperature of described carbonization is 700 ~ 900 DEG C, the time is 0.5 ~ 2h.
7. one kind utilizes activated carbon prepared by Hunan oil-tea camellia husks, it is characterised in that use the method described in any one of claim 1 ~ 6 to produce.
8. activated carbon as claimed in claim 7, it is characterised in that the aperture of described activated carbon is 3 ~ 4nm.
9. an activated carbon as claimed in claim 7 or 8 application in ultracapacitor.
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| CN106047508A (en) * | 2016-05-31 | 2016-10-26 | 福建师范大学 | Preparation method of detergent capable of removing fruit and vegetable pesticide residues |
| CN106276899A (en) * | 2016-08-19 | 2017-01-04 | 湖南农业大学 | Ultracapacitor carbon material prepared by a kind of fast-growing grass and production method thereof |
| CN110010358B (en) * | 2019-04-15 | 2020-11-06 | 南昌航空大学 | Preparation method of biomass porous carbon confinement transition metal sulfide loaded electrode material |
| CN110902677A (en) * | 2019-11-29 | 2020-03-24 | 金永哲 | Preparation method of activated carbon for decoloring adipic acid |
| CN112357920A (en) * | 2020-11-20 | 2021-02-12 | 大连民族大学 | Method for preparing activated carbon by using camellia oleifera shells as raw materials through microwave chemical activation method |
| CN112408390B (en) * | 2020-11-20 | 2022-10-18 | 西北化工研究院有限公司 | Method for preparing activated carbon adsorbent from kerosene co-refining residues |
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| JP4266711B2 (en) * | 2003-05-30 | 2009-05-20 | 株式会社カナック | Method and apparatus for producing activated carbon by microwave heating |
| CN102205960A (en) * | 2011-04-29 | 2011-10-05 | 河南省核力科技发展有限公司 | Method for preparing activated carbon electrode material for super capacitor |
| CN103435039A (en) * | 2013-08-20 | 2013-12-11 | 西安工程大学 | Method for preparing fallen phoenix tree leaf-doped muddy active carbon by microwave irradiation |
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| US9096439B2 (en) * | 2012-12-07 | 2015-08-04 | Wisys Technology Foundation, Inc. | Rapid, non-pyrolytic method of making activated carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4266711B2 (en) * | 2003-05-30 | 2009-05-20 | 株式会社カナック | Method and apparatus for producing activated carbon by microwave heating |
| CN102205960A (en) * | 2011-04-29 | 2011-10-05 | 河南省核力科技发展有限公司 | Method for preparing activated carbon electrode material for super capacitor |
| CN103435039A (en) * | 2013-08-20 | 2013-12-11 | 西安工程大学 | Method for preparing fallen phoenix tree leaf-doped muddy active carbon by microwave irradiation |
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