CN104445145B - A kind of simple method for preparing with hierarchical pore structure porous charcoal - Google Patents
A kind of simple method for preparing with hierarchical pore structure porous charcoal Download PDFInfo
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- CN104445145B CN104445145B CN201410663156.8A CN201410663156A CN104445145B CN 104445145 B CN104445145 B CN 104445145B CN 201410663156 A CN201410663156 A CN 201410663156A CN 104445145 B CN104445145 B CN 104445145B
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Abstract
The present invention discloses a kind of simple method for preparing with hierarchical pore structure porous charcoal. It is characterized in that: selection humic acids is raw material, mixing with KOH after fragmentation, screening, level porous charcoal is prepared in activation. Method steps is as follows: a, raw material prepare: after humic acids fragmentation, screening, collects the material that granularity is less than 2mm, with humic acids: the mass ratio of KOH=1:0.3 ~ 1.0 mixes, adds deionized water dipping 12h; B, activation: the material after dipping is placed in reactor, under nitrogen protection, with the ramp to 100 DEG C of 5 DEG C/min, constant temperature dehydration 0.5h, continues to be warming up to 800 DEG C, and constant temperature activation 1h, naturally cools to room temperature under nitrogen protection after terminating; C, product aftertreatment: by activation products successively through acidleach, be washed to neutrality, filtration drying, obtain level hole charcoal. The present invention can realize the regulation and control of pore structure, technique is simple, cheap, pollution-free, cost is low.
Description
Technical field
The present invention relates to a kind of simple method for preparing with hierarchical pore structure porous charcoal.
Background technology
Porous charcoal has high specific surface area, good electroconductibility, the chemical stability of acid-fast alkali-proof, and cheap, wide material sources. Carbonaceous presoma (such as coal, refinery coke, resin, biomass etc.) just can prepare gac by physically activated or chemical activation. The pore structure formed in reactivation process is often difficult to control, there is micropore (< 2nm), middle hole (2-50nm), and macropore (> 50nm), when the pore size distribution of porous charcoal have very strong regular time be called as level hole charcoal. Because it has unique pore structure feature, level hole charcoal is widely used in the fields such as absorption, catalysis, electrode materials. At present, the method synthesizing level hole charcoal mainly can be divided into three classes: 1. template; 2. template-activation integrated process; 3. direct synthesis technique. The basic ideas of template are, are filled in the duct of mould material by carbon precursor, and charcoal source is polymerized in template duct, then carbonize, remove template, obtain having the porous charcoal of orderly pore structure. According to the action character of template and template and carbon source, soft template method and hard template method can be divided into. Hard template mainly refers to the template with relative rigid structure, such as zeolite molecular sieve, aluminum oxide, mesoporous material and colloidal crystal etc.; Soft template method also claims organic-organic self-assembly method, refers to the aggregate that amphiphile, amphiphilic molecule or segmented copolymer are formed, such as micella, vesica, liquid crystal etc. Template be suitable for preparing have in, the porous charcoal of macroporous structure, and activation method is more suitable for micropore, adopt template-activation integrated process can synthesize have greatly-in-the level hole charcoal of micropore three grades of pore structures. Direct synthesis technique namely without template, select have level framework containing carbon thing, if animal skeleton, biomass etc. are as presoma, obtain level hole charcoal through charing or after activating. Although prepare each tool advantage of method of level hole charcoal above-mentioned, development potentiality is huge, but also there is respective defect. If hard template method many employings silicon oxide compound is as template, the strong acid such as hydrofluoric acid, sodium hydroxide solution, highly basic need to be used could to remove template, and technique is loaded down with trivial details, it is difficult to commercialization; Though organic formwork method is without the need to removing template, but template is expensive, and template easy depolymerization in carbonization process, Porosity control difficulty. Although template-activation integrated process successfully solves the problem of Porosity control, but technique is more complicated, cost is higher; The structure height of direct synthesizing porous charcoal depends on structure and the composition of presoma, cannot carry out artificial design and regulation and control. Therefore, preparing carbon layer secondary aperture charcoal material is the work having more challenge. On the basis guaranteeing level hole charcoal high-specific surface area, rationally pore size distribution, good electric conductivity, to be reduced process procedure as much as possible, to reduce preparation cost. This just needs to select presoma new, that be easy to design, explores new preparation synthetic method.
Summary of the invention
The object of the present invention provides a kind of simple method for preparing with hierarchical pore structure porous charcoal for weak point existing in above-mentioned prior art just. The method preparation technology is simple, it is not necessary to using a large amount of corrodibility activators, pollution-free, cost is low, is beneficial to batch production. Made level charcoal has unique hierarchical pore structure distribution: the micropore of 0.5-1.5nm, the middle hole of 3.0-5.0nm, and the macropore of micron level.
The object of the present invention realizes by following technical proposals:
The simple method for preparing with hierarchical pore structure porous charcoal of the present invention selects humic acids to be raw material, after broken, screening, mix with KOH and postactivated prepares level porous carbon material, and realization is to the regulation and control of pore structure, and its preparation methods steps is as follows:
A, raw material prepare: by humic acids by, after fragmentation, screening, collecting the material that granularity is less than 2mm, then with humic acids: the mass ratio of KOH=1:0.3 ~ 1.0 mixes, add deionized water dipping 12h;
B, activation: the material after dipping is placed in reactor, under nitrogen protection, is warming up to 100 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature dehydration 0.5h, then continues to be warming up to 800 DEG C, constant temperature activation 1h, activation naturally cools to room temperature after terminating under nitrogen protection;
C, product aftertreatment: by activation products successively through acidleach, be washed to neutrality, filtration drying, obtain level hole charcoal.
The useful effect of the present invention is as follows:
The present invention selects humic acids as presoma, by the activation of KOH mono-step, prepares level hole charcoal, and can realize the regulation and control of pore structure. Preparation technology is simple, and raw material sources is extensive, cheap, it is possible to carry out scale operation.
Embodiment
The present invention is described in further detail below with reference to embodiment:
Embodiment 1
A, by humic acids by, after broken, screening, collecting the material that granularity is less than 2mm, then by humic acids and KOH in mass ratio 1:0.3 carry out mixing and add deionized water and flood 12h;
B, mixture being placed in nickel reactor, under nitrogen protection, be warming up to 100 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature dehydration 0.5h, then continues to be warming up to 800 DEG C, constant temperature activation 1h, and activation naturally cools to room temperature after terminating under nitrogen protection;
C, products therefrom priority 5mol/LHCl dipping, deionized water are washed till neutrality, after drying under 110 DEG C of conditions, and obtained level hole charcoal.
Its BET specific surface area is 603m2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the middle hole of 3.0-5.0nm, and the macropore of micron level, and mesopore content is 27%.
Embodiment 2
A, by humic acids by, after broken, screening, collecting the material that granularity is less than 2mm, then by humic acids and KOH in mass ratio 1:0.5 carry out mixing and add deionized water and flood 12h;
B, mixture being placed in nickel reactor, under nitrogen protection, be warming up to 100 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature dehydration 0.5h, then continues to be warming up to 800 DEG C, constant temperature activation 1h, and activation naturally cools to room temperature after terminating under nitrogen protection;
C, products therefrom priority 5mol/LHCl dipping, deionized water are washed till neutrality, after drying under 110 DEG C of conditions, and obtained level hole charcoal.
Its BET specific surface area is 754m2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the middle hole of 3.0-5.0nm, and the macropore of micron level, and mesopore content is 49%.
Embodiment 3
A, by humic acids by, after broken, screening, collecting the material that granularity is less than 2mm, then by humic acids and KOH in mass ratio 1:0.7 carry out mixing and add deionized water and flood 12h;
B, mixture being placed in nickel reactor, under nitrogen protection, be warming up to 100 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature dehydration 0.5h, then continues to be warming up to 800 DEG C, constant temperature activation 1h, and activation naturally cools to room temperature after terminating under nitrogen protection;
C, products therefrom priority 5mol/LHCl dipping, deionized water are washed till neutrality, after drying under 110 DEG C of conditions, and obtained level hole charcoal.
Its BET specific surface area is 779m2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the middle hole of 3.0-5.0nm, and the macropore of micron level, and mesopore content is 69%.
Embodiment 4
A, by humic acids by, after broken, screening, collecting the material that granularity is less than 2mm, then by humic acids and KOH in mass ratio 1:0.9 carry out mixing and add deionized water and flood 12h;
B, mixture being placed in nickel reactor, under nitrogen protection, be warming up to 100 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature dehydration 0.5h, then continues to be warming up to 800 DEG C, constant temperature activation 1h, and activation naturally cools to room temperature after terminating under nitrogen protection;
C, products therefrom priority 5mol/LHCl dipping, deionized water are washed till neutrality, after drying under 110 DEG C of conditions, and obtained level hole charcoal.
Its BET specific surface area is 863m2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the middle hole of 3.0-5.0nm, and the macropore of micron level, and mesopore content is 57%.
Embodiment 5
A, by humic acids by, after broken, screening, collecting the material that granularity is less than 2mm, then by humic acids and KOH in mass ratio 1:1 carry out mixing and add deionized water and flood 12h;
B, mixture being placed in nickel reactor, under nitrogen protection, be warming up to 100 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature dehydration 0.5h, then continues to be warming up to 800 DEG C, constant temperature activation 1h, and activation naturally cools to room temperature after terminating under nitrogen protection;
C, products therefrom priority 5mol/LHCl dipping, deionized water are washed till neutrality, after drying under 110 DEG C of conditions, and obtained level hole charcoal.
Its BET specific surface area is 1137m2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the middle hole of 3.0-5.0nm, and the macropore of micron level, and mesopore content is 35%.
Claims (1)
1. one kind has the simple method for preparing of hierarchical pore structure porous charcoal, it is characterized in that: selection humic acids is raw material, after broken, screening, mix with KOH and postactivated prepare level porous carbon material, and realize the regulation and control to pore structure, preparation method's step is as follows:
A, raw material prepare: by humic acids by, after fragmentation, screening, collecting the material that granularity is less than 2mm, then with humic acids: the mass ratio of KOH=1:0.3 ~ 0.9 mixes, add deionized water dipping 12h;
B, activation: the material after dipping is placed in reactor, under nitrogen protection, is warming up to 100 DEG C with the temperature rise rate of 5 DEG C/min, constant temperature dehydration 0.5h, then continues to be warming up to 800 DEG C, constant temperature activation 1h, activation naturally cools to room temperature after terminating under nitrogen protection;
C, product aftertreatment: by activation products successively through acidleach, be washed to neutrality, filtration drying, obtain level hole charcoal, its structure distribution is: the micropore of 0.5-1.5nm, the middle hole of 3.0-5.0nm, and the macropore of micron level.
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| CN108529587B (en) * | 2017-08-30 | 2020-04-03 | 北京化工大学 | Preparation method and application of phosphorus-doped biomass graded porous carbon material |
| CN108962625A (en) * | 2018-06-22 | 2018-12-07 | 东莞理工学院 | A kind of supercapacitor carbon material and preparation method thereof prepared using humin as raw material |
| CN110078069A (en) * | 2019-03-28 | 2019-08-02 | 华南农业大学 | A kind of high-specific surface area level hole Carbon Materials and its low alkali number process for preparing activated and application |
| CN113135567B (en) * | 2021-04-28 | 2022-03-18 | 安徽工程大学 | Preparation method of activated carbon and product thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103373728A (en) * | 2012-04-16 | 2013-10-30 | 河南理工大学 | Method for preparing active carbon for super-capacitor from potassium humate in one-step carbonization way |
| CN103641117A (en) * | 2013-12-17 | 2014-03-19 | 中国科学院新疆理化技术研究所 | Method for preparing activated carbon material with humic acid as raw material and application of activated carbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103373728A (en) * | 2012-04-16 | 2013-10-30 | 河南理工大学 | Method for preparing active carbon for super-capacitor from potassium humate in one-step carbonization way |
| CN103641117A (en) * | 2013-12-17 | 2014-03-19 | 中国科学院新疆理化技术研究所 | Method for preparing activated carbon material with humic acid as raw material and application of activated carbon material |
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