CN104445145A - Simple preparation method of porous carbon with hierarchical pore structure - Google Patents
Simple preparation method of porous carbon with hierarchical pore structure Download PDFInfo
- Publication number
- CN104445145A CN104445145A CN201410663156.8A CN201410663156A CN104445145A CN 104445145 A CN104445145 A CN 104445145A CN 201410663156 A CN201410663156 A CN 201410663156A CN 104445145 A CN104445145 A CN 104445145A
- Authority
- CN
- China
- Prior art keywords
- activation
- pore structure
- nitrogen protection
- koh
- constant temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a simple preparation method of porous carbon with a hierarchical pore structure. The simple preparation method is characterized in that humic acid is used as a raw material, broken and sieved, and then mixed with KOH, and activated to prepare the hierarchical porous carbon. The method comprises the following steps: a, raw material preparation: breaking and sieving humic acid, collecting materials with a granularity of less than 2mm, mixing in a mass ratio of humic acid to KOH of 1: (0.3 to 1.0), and adding deionized water to be soaked for 12 hours; b, activation: placing the soaked materials in a reaction kettle, heating to 100 DEG C at a speed of 5 DEG C/min under nitrogen protection, dehydrating for 0.5 hours at a constant temperature, further heating to 800 DEG C, activating for 1 hour at a constant temperature, then naturally cooling to a room temperature under the nitrogen protection; c, product aftertreatment: sequentially carrying out acid leaching on the activated product, washing to be neutral, filtering and drying to obtain the hierarchical pore carbon. The method disclosed by the invention is capable of realizing the adjustment and control of the pore structure, simple in process, low in price, pollution-free and low in cost.
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 (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), mesopore (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 property, level hole charcoal is widely used in the fields such as absorption, catalysis, electrode materials.At present, the method for synthesizing level hole charcoal mainly can be divided three classes: 1. template; 2. template-activation integrated process; 3. direct synthesis technique.The basic ideas of template are, are filled into by carbon precursor in the duct of mould material, charcoal source is polymerized in template duct, then carbonizes, remove template, obtain the porous charcoal with 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, 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, as micella, vesica, liquid crystal etc.During template is suitable for preparing and has, the porous charcoal of macroporous structure, and activation method is more suitable for micropore, adopts template-activation integrated process to synthesize to have greatly-in-the level hole charcoal of micropore three grades of pore structures.Direct synthesis technique, namely without template, selects the carbon containing thing with level framework, if animal skeleton, biomass etc. are as presoma, after charing or activation, obtains level hole charcoal.Although each tool advantage of method of above-mentioned prepared layer secondary aperture charcoal, development potentiality is huge, 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 be used to remove template, and technique is loaded down with trivial details, is difficult to commercialization; Though organic formwork method is without the need to removing template, template expensive, and template easy depolymerization in carbonization process, Porosity control difficulty.Although template-activation integrated process successfully solves the problem of Porosity control, technique is more complicated, and 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, prepare carbon layer secondary aperture Carbon Materials to be one and to have more challenging work.On the basis of guaranteeing level hole charcoal high-specific surface area, rationally pore size distribution, good electric conductivity, process procedure to be reduced as much as possible, reduces preparation cost.This just needs to select presoma that is new, that be easy to design, explores new preparation synthetic method.
Summary of the invention
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, does not need to use a large amount of corrodibility activators, and 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 mesopore of 3.0-5.0nm, and the macropore of micron level.
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 postactivatedly prepare level porous carbon material with KOH, and the regulation and control of realization to pore structure, its preparation methods steps is as follows:
A, raw material prepare: by humic acids by after fragmentation, screening, collect 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, after activation terminates, naturally cool to room temperature under nitrogen protection;
C, product aftertreatment: by activation products successively through acidleach, be washed to neutrality, filtration drying, obtain level hole charcoal.
Beneficial 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, can 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, collect 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 is placed in nickel 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, and constant temperature activation 1h, after activation terminates, naturally cools to room temperature under nitrogen protection;
C, products therefrom priority 5mol/L HCl 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 603m
2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the mesopore 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, collect 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 is placed in nickel 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, and constant temperature activation 1h, after activation terminates, naturally cools to room temperature under nitrogen protection;
C, products therefrom priority 5mol/L HCl 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 754m
2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the mesopore 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, collect 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 is placed in nickel 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, and constant temperature activation 1h, after activation terminates, naturally cools to room temperature under nitrogen protection;
C, products therefrom priority 5mol/L HCl 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 779m
2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the mesopore 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, collect 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 is placed in nickel 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, and constant temperature activation 1h, after activation terminates, naturally cools to room temperature under nitrogen protection;
C, products therefrom priority 5mol/L HCl 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 863m
2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the mesopore 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, collect 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 is placed in nickel 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, and constant temperature activation 1h, after activation terminates, naturally cools to room temperature under nitrogen protection;
C, products therefrom priority 5mol/L HCl 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 1137m
2/ g, aperture integrated distribution exists: the micropore of 0.5-1.5nm, the mesopore 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 postactivatedly prepare level porous carbon material, and the regulation and control realized pore structure, preparation method's step is as follows:
A, raw material prepare: by humic acids by after fragmentation, screening, collect 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, after activation terminates, naturally cool to room temperature under nitrogen protection;
C, product aftertreatment: by activation products successively through acidleach, be washed to neutrality, filtration drying, obtain level hole charcoal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410663156.8A CN104445145B (en) | 2014-11-20 | 2014-11-20 | A kind of simple method for preparing with hierarchical pore structure porous charcoal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410663156.8A CN104445145B (en) | 2014-11-20 | 2014-11-20 | A kind of simple method for preparing with hierarchical pore structure porous charcoal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104445145A true CN104445145A (en) | 2015-03-25 |
| CN104445145B CN104445145B (en) | 2016-06-01 |
Family
ID=52892009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410663156.8A Active CN104445145B (en) | 2014-11-20 | 2014-11-20 | A kind of simple method for preparing with hierarchical pore structure porous charcoal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104445145B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529587A (en) * | 2017-08-30 | 2018-09-14 | 北京化工大学 | A kind of preparation method and applications of the biomass graded hole Carbon Materials of phosphorus doping |
| 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 |
| CN113135567A (en) * | 2021-04-28 | 2021-07-20 | 安徽工程大学 | Preparation method of activated carbon and product thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-11-20 CN CN201410663156.8A patent/CN104445145B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529587A (en) * | 2017-08-30 | 2018-09-14 | 北京化工大学 | A kind of preparation method and applications of the biomass graded hole Carbon Materials of phosphorus doping |
| 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 |
| CN113135567A (en) * | 2021-04-28 | 2021-07-20 | 安徽工程大学 | Preparation method of activated carbon and product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104445145B (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104528720B (en) | The preparation method of a kind of multi-stage porous Carbon Materials and product | |
| CN104709906B (en) | Preparation method of three dimensional graded porous activated carbon material | |
| CN102992282B (en) | Mesoporous C3N4 photocatalytic material prepared by using molten salt method and application thereof in photocatalysis field | |
| CN111115631B (en) | High-mechanical-strength coffee-grounds-based molded porous carbon material and preparation method thereof | |
| CN101618869B (en) | Method for preparing small-size meso-porous hollow carbon sphere | |
| CN104445145B (en) | A kind of simple method for preparing with hierarchical pore structure porous charcoal | |
| CN101177266A (en) | Preparation method of active carbon electrode material for super capacitor | |
| CN105936503B (en) | A kind of three-dimensional graphite carbon material rich in continuous meso-hole structure and preparation method thereof | |
| CN106145132B (en) | A method of ordered mesoporous material Al-MCM-41 is prepared using attapulgite | |
| CN101538034B (en) | Preparation method of one-step synthesis carbon ball | |
| CN102674346A (en) | Process for preparing high-specific surface area composite pore structure coal-based activated carbon by using low dosage of KOH | |
| CN112225216A (en) | Medium-micropore lignin-based activated carbon and preparation method thereof | |
| CN104248986A (en) | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate | |
| CN103121698A (en) | Method for synthesizing SAPO (silicoaluminophosphate)-34 by solid-phase grinding | |
| CN106925239A (en) | A kind of novel drier and preparation method thereof | |
| CN105883805B (en) | A kind of preparation method of the high-specific surface area carbosphere based on tea seed shell base | |
| CN107694515B (en) | A kind of porous carbon of Nitric Acid Modified and its application | |
| CN108383136A (en) | The preparation method of nucleocapsid SSZ-13@Nano SSZ-13 molecular sieves | |
| CN106430144A (en) | Method for preparing asphalt-based hierarchical porous carbon sheet based on sheet-shaped magnesium oxide template and application thereof | |
| CN101531375A (en) | Method for synthesizing bimodal silicon-aluminum mesoporous material | |
| CN110227456A (en) | MOFs derives two-dimensional multistage hole Cu/C composite material and preparation method | |
| CN107720724B (en) | Nano porous carbon material with high specific surface area and preparation method thereof | |
| CN103318891B (en) | Method for generating one-dimensional silicon carbide nanowires on multiporous charcoal template | |
| CN106241770B (en) | A kind of preparation method of bamboo base porous carbon | |
| CN107814393A (en) | A kind of method of rapid crystallization synthesis EMT molecular sieves |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |