CN101012058A - Method for preparing medium pore carbon of narrow aperture and high degree of graphitization - Google Patents
Method for preparing medium pore carbon of narrow aperture and high degree of graphitization Download PDFInfo
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Abstract
The invention discloses a making method of narrow-aperture high-graphitizing degree middle-hole carbon, which comprises the following steps: allocating metal compound and carbon primer with weight rate at 0.1-6:1; dissolving metal compound in the solution with carbon primer; stripping solvent; solidifying in the air for 0.1-20h under 80-400 deg.c; charring for 0.1-3h under inert gas at 500-1200 deg.c; proceeding acid washing until the metal element is not detected; obtaining the product.
Description
Technical field
The invention belongs to a kind of preparation method of porous charcoal, relate in particular to the preparation method of a kind of narrow pore size distribution, porous charcoal that degree of graphitization is high.
Background technology
Porous charcoal is applied in absorption, support of the catalyst widely owing to have high-specific surface area, abundant hole and resistance to acids and bases, chromatographic column is separated and aspects such as electrode of super capacitor.Narrow pore size distribution is vital to the aspects such as utilising efficiency that improve absorption, chromatographic column separation efficiency and ultracapacitor.Simultaneously, high conductivity also is indispensable for the application of ultracapacitor.The preparation method of porous charcoal mainly contains physical activation method, chemical activation method, catalytic activation method and template.Physical activation method, chemical activation method and catalytic activation method can be prepared the porous charcoal of high-specific surface area by suitable process conditions, but the pore size distribution broad.Template is divided organic formwork method and inorganic template: the organic formwork method is that two kinds of different organic compound of thermostability are mixed, and only through charing Processing of Preparation porous charcoal, this method preparation technology is simple, but the porous charcoal pore size distribution of preparation is not really concentrated; Inorganic template is a kind of effective ways of regulating and control the porous charcoal pore structure, specifically is that carbon precursors such as heat-reactive phenolic resin resin, sucrose and furfuryl alcohol are incorporated in the molecular sieve template, removes the preparation porous charcoal through charing, template.Though this method can be controlled the pore structure of mesopore charcoal, need synthetic molecular sieve template, and can't prepare the high porous charcoal of degree of graphitization.Recently, (Catalytic graphitization of templated mesoporous carbons.Carbon.44 (2006): 468-474) propose on the basis of template such as Marta Sevilla, metal is introduced in the porous charcoal, to reach the purpose of catalyzed graphitization.But this arts demand prepares porous charcoal with inorganic template in advance, complicated process of preparation, product cost height, the finished product pore size distribution broad.
Summary of the invention
The invention provides the preparation method of low, the narrow pore size distribution of a kind of cost of material, the high porous charcoal of degree of graphitization.
The present invention adopts metallic compound to do template compound, and pore-creating and catalyzed graphitization effect are carried out simultaneously.Its core is the selection of metallic compound and carbon precursor, and the part metals compound decomposes in the carbon precursor solidification process, generates metal oxide, produces the part hole in the gas evolution process.The reaction of metal oxide and charcoal generates metal carbide or simple substance in the carbonization process, and the burning of charcoal is lost and produced a large amount of holes in this course, and the existence of metal then makes the carbon matrix degree of graphitization improve.
Preparation method of the present invention is as follows:
Mass ratio by metal compound and carbon precursor is 0.1-6: 1, metallic compound is dissolved in the solution that is dissolved with carbon precursor, remove behind the solvent in air 80-400 ℃ and solidify 0.1-20h, 500-1200 ℃ of charing 0.1-3h under the inert atmosphere, pickling makes narrow pore size distribution, porous charcoal that degree of graphitization is high till detecting less than metallic element.
Aforesaid metallic compound is alkaline earth metal compound or transistion metal compound.Alkaline earth metal compound is magnesium nitrate, lime carbonate, magnesiumcarbonate etc.Transistion metal compound is nickelous nitrate, Xiao Suangu, iron nitrate or iron(ic) chloride etc.
Aforesaid carbon precursor is organic soluble polymers such as heat-reactive phenolic resin, pitch, polyacrylonitrile or sucrose.
The dimethyl sulphoxide solution of the ethanolic soln that the aforesaid solution that is dissolved with carbon precursor is heat-reactive phenolic resin, bituminous toluene solution, polyacrylonitrile or organic soluble polymers such as the aqueous solution of sucrose.
Aforesaid acid is nitric acid, hydrochloric acid, sulfuric acid etc.
The present invention compared with prior art has following advantage:
(1) preparation method is simple.
(2) even select difficult graphited raw material for use, low temperature can prepare the high porous charcoal of degree of graphitization down.
(3) Zhi Bei porous charcoal pore size distribution is narrow, can select suitable metallic compound by pore size distribution as required.
(4) product cost is low.
Embodiment
Embodiment 1
Magnesium nitrate is added in the ethanolic soln of heat-reactive phenolic resin resin, the mass ratio of magnesium nitrate and heat-reactive phenolic resin is 0.1: 1, removes solvent, and 80 ℃ solidify 0.1h, the following 500 ℃ of charing 0.1h of inert atmosphere, nitric acid wash till detecting less than metallic element and obtain product.Product performance index sees Table 1.
Embodiment 2
Nickelous nitrate is added in the bituminous toluene solution, and nickelous nitrate and bituminous mass ratio are 2: 1, remove solvent, and 200 ℃ solidify 1h, the following 900 ℃ of charing 1h of inert atmosphere, and the salt pickling obtains product till detecting less than metallic element.Product performance index sees Table 1.
Embodiment 3
Iron nitrate is added in the dimethyl sulphoxide solution of polyacrylonitrile, the mass ratio of iron nitrate and polyacrylonitrile is 6: 1, removes solvent, and 400 ℃ solidify 5h, the following 1200 ℃ of charing 3h of inert atmosphere, and sulfuric acid washing obtains product till detecting less than metallic element.Product performance index sees Table 1.
Embodiment 4
Xiao Suangu is added in the aqueous solution of sucrose, the mass ratio of Xiao Suangu and sucrose is 3: 1, removes solvent, and 100 ℃ solidify 8h, and the following 900 ℃ of charing 1h of inert atmosphere, nitric acid wash till detecting less than metallic element and obtain product.Product performance index sees Table 1.
Embodiment 5
Lime carbonate is added in the ethanolic soln of heat-reactive phenolic resin resin, the mass ratio of lime carbonate and heat-reactive phenolic resin is 4: 1, removes solvent, and 300 ℃ solidify 10h, the following 800 ℃ of charing 1h of inert atmosphere, sulfuric acid wash till detecting less than metallic element and obtain product.Product performance index sees Table 1.
Embodiment 6
Magnesiumcarbonate is added in the aqueous solution of sucrose, the mass ratio of magnesiumcarbonate and sucrose is 1: 1, removes solvent, and 150 ℃ solidify 20h, 900 ℃ of following charing 1.5h, and the salt pickling obtains product till detecting less than metallic element.Product performance index sees Table 1.
Embodiment 7
Iron(ic) chloride is added in the aqueous solution of sucrose, the mass ratio of iron(ic) chloride and sucrose is 1.5: 1, removes solvent, and 150 ℃ solidify 15h, the following 900 ℃ of charing 1.5h of inert atmosphere, and the salt pickling obtains product till detecting less than metallic element.Product performance index sees Table 1.
The performance index of table 1 porous charcoal
| Embodiment | BET specific surface area (m 2/g) | Pore volume (cm 3/g) | BJH pore size distribution half-peak height wide (nm) | Degree of graphitization (%) |
| 1 | 121 | 0.37 | 0.57 | 9 |
| 2 | 354 | 0.71 | 0.53 | 65 |
| 3 | 660 | 0.83 | 0.56 | 51 |
| 4 | 834 | 1.18 | 0.67 | 41 |
| 5 | 520 | 0.90 | 0.45 | 23 |
| 6 | 486 | 0.78 | 0.47 | 27 |
| 7 | 567 | 0.96 | 0.52 | 39 |
Claims (7)
1. the preparation method of a narrow aperture, mesopore charcoal that degree of graphitization is high is characterized in that comprising the steps:
Mass ratio by metal compound and carbon precursor is 0.1-6: 1, metallic compound is dissolved in the solution that is dissolved with carbon precursor, remove behind the solvent in air 80-400 ℃ and solidify 0.1-20h, 500-1200 ℃ of charing 0.1-3h under the inert atmosphere, pickling makes narrow pore size distribution, porous charcoal that degree of graphitization is high till detecting less than metallic element.
2, the preparation method of a kind of narrow aperture as claimed in claim 1, mesopore charcoal that degree of graphitization is high is characterized in that described metallic compound is alkaline earth metal compound or transistion metal compound.
3, the preparation method of a kind of narrow aperture as claimed in claim 2, mesopore charcoal that degree of graphitization is high is characterized in that described alkaline earth metal compound is magnesium nitrate, lime carbonate or magnesiumcarbonate.
4, the preparation method of a kind of narrow aperture as claimed in claim 2, mesopore charcoal that degree of graphitization is high is characterized in that described transistion metal compound is nickelous nitrate, Xiao Suangu, iron nitrate or iron(ic) chloride.
5, the preparation method of a kind of narrow aperture as claimed in claim 1, mesopore charcoal that degree of graphitization is high is characterized in that described carbon precursor is heat-reactive phenolic resin, pitch, polyacrylonitrile or sucrose.
6, the preparation method of a kind of narrow aperture as claimed in claim 1, mesopore charcoal that degree of graphitization is high is characterized in that the described solution that is dissolved with carbon precursor is the dimethyl sulphoxide solution of the ethanolic soln of heat-reactive phenolic resin, bituminous toluene solution, polyacrylonitrile or the aqueous solution of sucrose.
7, the preparation method of a kind of narrow aperture as claimed in claim 1, mesopore charcoal that degree of graphitization is high is characterized in that described acid is nitric acid, hydrochloric acid or sulfuric acid.
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| CN102007629A (en) * | 2008-02-19 | 2011-04-06 | 卡伯特公司 | High surface area graphitized carbon and processes for making same |
| CN102280262A (en) * | 2011-01-24 | 2011-12-14 | 青岛大学 | Porous carbon electrode material and preparing method thereof |
| CN102464333A (en) * | 2010-11-04 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve by in-situ crystallization |
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