CN1395988A - Process for preparing carbon aerogel - Google Patents
Process for preparing carbon aerogel Download PDFInfo
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- CN1395988A CN1395988A CN 01120419 CN01120419A CN1395988A CN 1395988 A CN1395988 A CN 1395988A CN 01120419 CN01120419 CN 01120419 CN 01120419 A CN01120419 A CN 01120419A CN 1395988 A CN1395988 A CN 1395988A
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- charcoal
- aero gel
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Abstract
A carbon aerogel is prepared from asphalt, intermediate-phase asphalt and crude coke as raw materials through nitriding and oxidizing reaction by use of the mixture of concentrated sulfuric acid and concentrated nitric acid, alkali dissolving for removing insoluble substances, adding strong acid deposition, washing, drying to obtain the presoma, and heating to 220-300 deg.C for producing explosion. Its advantages are low cost, short period, fine granularity, and high specific surface area.
Description
The invention belongs to a kind of method for preparing charcoal-aero gel, relate in particular to a kind of method for preparing charcoal-aero gel with explosion method.
Charcoal-aero gel is the nanometer porous property of an a kind of novel light amorphous carbon material, and its voidage is up to 80～98%, and typical void size is less than 50nm, and particle size is less than 20nm, specific area 600～1000m
2/ g, density is 0.05～0.80g/cm
3, charcoal-aero gel also has other many advantages concurrently in addition, is a kind of new material that has many excellent properties and broad prospect of application is arranged.Charcoal-aero gel has high-specific surface area, high voidage, low bulk density, good stability, resistance to chemical attack, conductance is low, characteristics such as the variable density scope is wide, thereby can be used as multiple functional material, as catalyst and catalyst carrier, super capacitor material, low Heat Conduction Material, electrochemical electrode material, gas cleaning and parting material etc.
The preparation process of charcoal-aero gel generally was divided into for three steps, the formation of promptly organic charcoal gel, supercritical drying and carbonization process.The preparation flow of this technology is: resorcinol, formaldehyde and catalyst are mixed according to a certain percentage, and reaction under certain condition forms organosol, and aging back forms organogel; After water in this gel and acetone or alcohol exchange, to carry out supercritical drying and make organic aerogel, last charing promptly gets charcoal-aero gel.The preparation flow of this project is seen Fig. 1.
There is following problem in this preparation process: (1) raw material (being mainly resorcinol and formaldehyde at present) is more expensive; (2) preparation technology is loaded down with trivial details, manufacturing cycle is long.It is long mainly to show as the collosol and gel cycle, and the swap time of water in the gel and organic solvent and carbon dioxide is long; (3) adopt Supercritical Drying Technology, need high-tension apparatus, thereby the cost height.
In the plain meeting of two annual charcoal in 1987, Fujii etc. (405 pages of collections of thesis) have reported that the carbonaceous material of being made up of condensed-nuclei aromatics is (as pitch, mesophase pitch, green coke) after oxidations such as nitric acid/sulfuric acid or hydrogen peroxide, nitrated or sulfonation, is converted into the water-based mesophase pitch method that dissolves in alkaline solution.Tateishi etc. are at Catbon, and 1991,29 volumes were gone up for 1296 pages and reported that the water-based mesophase pitch dissolves in ammoniacal liquor and changes gel into.People such as Li Xuanke have reported on 57 pages of " novel charcoal material " 2000 15 1 phases of volume and have utilized this method to prepare charcoal-aero gel, preparation technology's flow process of this charcoal-aero gel is: with the charcoal source, as pitch, mesophase pitch or green coke etc., by a certain percentage with oxidant hybrid reactions such as the concentrated sulfuric acid and red fuming nitric acid (RFNA) or hydrogen peroxide, after the reaction oxidized asphalt is diluted, filters, washs, with NaOH sepage dissolving, acid such as hydrochloric acid precipitation makes the water-based mesophase pitch again; This water-based mesophase pitch is dissolved in organosols such as ethylene glycol, is converted into organogel after wearing out; After ethylene glycol in this gel and ethanol exchange, carry out drying with Supercritical Ethanol and make organic aerogel, the further aging charcoal-aero gel that obtains.Its preparation technology's flow process is seen Fig. 2.
The preparation method of above-mentioned preparation charcoal-aero gel method and preceding described phenolic aldehyde aeroge roughly the same though adopted cheap pitch etc. to be raw material, also exists manufacturing cycle long, shortcomings such as employing supercritical drying expense height.
The purpose of this invention is to provide the method for preparing charcoal-aero gel that a kind of manufacturing cycle is short, operating cost is low.
The object of the present invention is achieved like this, utilize pitch, mesophase pitch, green coke to be raw material, the mixture of the process concentrated sulfuric acid and red fuming nitric acid (RFNA) is that nitrating agent and oxidant carry out nitrated and oxidation reaction, again through the molten insoluble matter of removing of alkali, add the strong acid precipitation, the washing drying and other steps predecessor that must explode.The blast predecessor is heated, blast, promptly get charcoal-aero gel at 220～300 ℃.Then also can be to its suitable heat treatment.
Preparation method of the present invention comprises the steps:
(1) pitch or the green coke of granularity less than 0.2mm mixed in the ratio of pitch or green coke: oxidant=1Kg: 10～30L with oxidant, in oxidizing temperature is under 30～90 ℃ of conditions, oxidation 0.1～4 hour, cessation reaction is diluted with cold water in the reaction back, after the cooling, filter, sediment is washed pH=4～7 to washing lotion with deionized water;
(2) sediment after will washing joins in NaOH or the KOH solution, makes pH＞12 of solution, stirs in 60～90 ℃ temperature 0.5～6 hour, filters, and obtains the filtrate of property of water-bearing mesophase pitch;
(3) give adding hydrochloric acid or nitric acid in the filtrate of property of water-bearing mesophase pitch, make pH＜1.8 of solution, centrifugation obtains sediment; Sediment is spent deionised water, and then 100 ℃ of oven dry, predecessor must explode;
(4) will explode predecessor by explosive: reactor=1Kg: 10～1000L puts into reactor, use the inert gas purge reactor, firing rate with 2～50 ℃/min heats then, is heated to 220～300 ℃ and blasts, and finally makes charcoal-aero gel.
Aforesaid oxidant is that the concentrated sulfuric acid of the red fuming nitric acid (RFNA) of 60-67% and 90-98% is by 1: 1.5～4 mixtures of forming.
The charcoal-aero gel bulk density that the present invention makes is 0.02～0.4g/cm
3, specific area is 400～1100m
2/ g, the particle size of network is 1～30nm, pore size distribution is mainly micropore, less than 2nm.
The present invention compared with prior art has following advantage:
(1) be the charcoal source with pitch, mesophase pitch, green coke, raw material is inexpensive, is easy to get.
(2) manufacturing cycle is short.
(3) production cost is low.
(4) carbon aerogel particle of explosion method preparation is tiny, specific area big, pore size distribution is mainly micropore, bulk density is little.
Embodiments of the invention are as follows:
Embodiment 1:
5.0 gram high temperature coal-tar pitches (108 ℃ of softening points) are joined among the mixed solution 100ml that volume ratio is 1: 3 60% red fuming nitric acid (RFNA) and 98% concentrated sulfuric acid, 30 ℃ of stirred in water bath 4 hours, to stir liquid joins in the 500ml cold water, shake all, filter, leaching thing washs to pH=7.0, NaOH solution with 100ml1mol/l dissolves again, and under 60 ℃ of conditions, stirred 1 hour, cooled and filtered is collected filtrate, regulates the acidity of filtrate with 1mol/l hydrochloric acid, make its PH=1.5, filter, wash, will be deposited in 110 ℃ of oven dry, predecessor 7.1g must explode.
Get 1.39g blast predecessor and put into the 1L reactor, purge with Ar, in Ar atmosphere (90ml/min) heating down of flowing, 10 ℃/min of firing rate blasts at 285 ℃, charcoal-aero gel.With charcoal-aero gel under Ar atmosphere, with the programming rate of 10 ℃/mind, at 500 ℃ of constant temperature 1h, the charcoal-aero gel after must calcining, 0.77g.Analysis result shows: specific area is 614m
2/ g, average pore size 1.57nm, bulk density are 0.19g/ml, structure is a microporous mesh.
Embodiment 2:
5.0 gram high temperature coal-tar pitches (108 ℃ of softening points) are joined among the mixed solution 150ml of 1: 4 67% red fuming nitric acid (RFNA) and 90% concentrated sulfuric acid, 50 ℃ of stirred in water bath 1 hour, to stir liquid joins in the 500ml cold water, shake all, filter, leaching thing washs to PH=6.0, NaOH solution with 100ml 1mol/l dissolves again, and under 80 ℃ of conditions, stirred 1 hour, cooled and filtered is collected filtrate, regulates the acidity of filtrate with 1mol/l hydrochloric acid, make its PH=1.8, filter, wash, will be deposited in 110 ℃ of oven dry, predecessor 7.2g must explode.
Get 1.14g blast predecessor and put into the 1L reactor, purge with Ar, in Ar atmosphere (90ml/min) heating down of flowing, 10 ℃/min of firing rate blasts about 290 ℃, charcoal-aero gel 0.66g.Again with charcoal-aero gel under Ar atmosphere, with the programming rate of 5 ℃/min, at 500 ℃ of constant temperature 1h, the charcoal-aero gel 0.60g after must calcining.Analysis result shows: specific area is 675m
2/ g, average pore size 1.6nm, bulk density are 0.20g/ml, structure is a microporous mesh.
Embodiment 3:
5.0 gram high temperature coal-tar pitches (108 ℃ of softening points) are joined among the mixed solution 100ml of 3: 7 68% red fuming nitric acid (RFNA) and 98% concentrated sulfuric acid, 80 ℃ of stirred in water bath 1 hour, to stir liquid joins in the 500ml cold water, shake all, filter, leaching thing washs to PH=6.0, KOH solution with 100ml 1mol/l dissolves again, and under 80 ℃ of conditions, stirred 1 hour, cooled and filtered is collected filtrate, regulates the acidity of filtrate with 1mol/l nitric acid, make its PH=1.5, filter, wash, will be deposited in 110 ℃ of oven dry, predecessor 6.4g must explode.
Get 0.98g blast predecessor and put into the 0.5L reactor, purge with Ar, in Ar atmosphere (90ml/min) heating down of flowing, 10 ℃/min of firing rate blasts at 276 ℃, charcoal-aero gel.With charcoal-aero gel under Ar atmosphere, with the programming rate of 10 ℃/min, at 500 ℃ of constant temperature 1h, the charcoal-aero gel 0.65g after must calcining.Analysis result shows: specific area is 953m
2/ g, average pore size 1.58nm, bulk density are 0.05g/ml, structure is a microporous mesh.
Embodiment 4:
5.0 gram oil mesophase pitch are joined among the mixed solution 150ml of 1: 1.5 66% red fuming nitric acid (RFNA) and 98% concentrated sulfuric acid, 50 ℃ of stirred in water bath 0.1 hour, to stir liquid joins in the 500ml cold water, shake all, filter, leaching thing washs to PH=6.1, NaOH solution with 100ml 1mol/l dissolves again, and under 70 ℃ of conditions, stirred 1 hour, cooled and filtered is collected filtrate, regulates the acidity of filtrate with 1mol/l hydrochloric acid, make its PH=1.8, filter, wash, will be deposited in 110 ℃ of oven dry, predecessor 7.0g must explode.
Get 1.1g blast predecessor and put into the 500ml reactor, purge with Ar, in Ar atmosphere (90ml/min) heating down of flowing, 2 ℃/min of firing rate blasts about 282 ℃, charcoal-aero gel.With charcoal-aero gel under Ar atmosphere, with the programming rate of 10 ℃/min, at 500 ℃ of constant temperature 1h, the charcoal-aero gel after must calcining, 0.52g.Analysis result shows: specific area is 644m
2/ g, average pore size 1.6nm, bulk density are 0.18g/ml, structure is a microporous mesh.
Embodiment 5:
The preparation of blast predecessor is with embodiment 3.Charcoal-aero gel after just will exploding under Ar atmosphere, with the programming rate of 5 ℃/min, is heated to 1000 ℃, and constant temperature 1h, naturally cooling.
Analysis result shows: specific area is 904m
2/ g, average pore size 1.6nm, bulk density are 0.08g/ml, structure is a microporous mesh.
Embodiment 6:
The preparation of blast predecessor is with embodiment 3.Get 0.98g blast predecessor and put into the 15ml reactor, use the Ar displaced air,, blast, get charcoal-aero gel at 298 ℃ then with 50 ℃/min of firing rate.With charcoal-aero gel under Ar atmosphere, with the programming rate of 2 ℃/min, at 600 ℃ of constant temperature 1h, the charcoal-aero gel 0.63g after must calcining.Analysis result shows: specific area is 922m
2/ g, average pore size 1.61nm, bulk density are 0.06g/ml, structure is a microporous mesh.
Claims (2)
1. a method for preparing charcoal-aero gel is characterized in that the preparation method comprises the steps:
(1) pitch or the green coke of granularity less than 0.2mm mixed in the ratio of pitch or green coke: oxidant=1Kg: 10～30L with oxidant, in oxidizing temperature is under 30～90 ℃ of conditions, oxidation 0.1～4 hour, cessation reaction is diluted with cold water in the reaction back, after the cooling, filter, sediment is washed pH=4～7 to washing lotion with deionized water;
(2) sediment after will washing joins in NaOH or the KOH solution, makes pH＞12 of solution, stirs in 60～90 ℃ temperature 0.5～6 hour, filters, and obtains the filtrate of property of water-bearing mesophase pitch;
(3) give adding hydrochloric acid or nitric acid in the filtrate of property of water-bearing mesophase pitch, make pH＜1.8 of solution, centrifugation obtains sediment; Sediment is spent deionised water, and then 100 ℃ of oven dry, predecessor must explode;
(4) will explode predecessor by explosive: reactor=1Kg: 10～1000L puts into reactor, use the inert gas purge reactor, firing rate with 2～50 ℃/min heats then, is heated to 220～300 ℃ and blasts, and finally makes charcoal-aero gel.
2. a kind of method for preparing charcoal-aero gel as claimed in claim 1 is characterized in that described oxidant is that the concentrated sulfuric acid of the red fuming nitric acid (RFNA) of 60-67% and 90-98% is by 1: 1.5～4 mixtures of forming.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011204192A CN1135136C (en) | 2001-07-12 | 2001-07-12 | Process for preparing carbon aerogel |
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|---|---|---|---|
| CNB011204192A CN1135136C (en) | 2001-07-12 | 2001-07-12 | Process for preparing carbon aerogel |
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| CN1395988A true CN1395988A (en) | 2003-02-12 |
| CN1135136C CN1135136C (en) | 2004-01-21 |
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|---|---|---|---|
| CNB011204192A Expired - Fee Related CN1135136C (en) | 2001-07-12 | 2001-07-12 | Process for preparing carbon aerogel |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649477B (en) * | 2009-09-11 | 2011-04-06 | 中国工程物理研究院激光聚变研究中心 | Preparation method of metal carbon aerogel composite material |
| CN102294255A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Carbon gel catalyst and application thereof |
| CN102390826A (en) * | 2011-07-14 | 2012-03-28 | 华东理工大学 | Carbon aerogel surface modification method |
| CN103551089A (en) * | 2013-10-14 | 2014-02-05 | 上海应用技术学院 | Copper oxide/carbon hybrid aerogel material and its preparation method and application thereof |
| CN105885907A (en) * | 2016-05-05 | 2016-08-24 | 天津工业大学 | Preparation method for general-purpose pitch-based carbon fiber spinning pitch |
| CN107963619A (en) * | 2017-11-14 | 2018-04-27 | 石河子大学 | A kind of lightweight electromagnetic wave absorbing material and preparation method thereof |
-
2001
- 2001-07-12 CN CNB011204192A patent/CN1135136C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649477B (en) * | 2009-09-11 | 2011-04-06 | 中国工程物理研究院激光聚变研究中心 | Preparation method of metal carbon aerogel composite material |
| CN102294255A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Carbon gel catalyst and application thereof |
| CN102294255B (en) * | 2010-06-25 | 2014-08-06 | 中国科学院大连化学物理研究所 | Carbon gel catalyst and application thereof |
| CN102390826A (en) * | 2011-07-14 | 2012-03-28 | 华东理工大学 | Carbon aerogel surface modification method |
| CN103551089A (en) * | 2013-10-14 | 2014-02-05 | 上海应用技术学院 | Copper oxide/carbon hybrid aerogel material and its preparation method and application thereof |
| CN103551089B (en) * | 2013-10-14 | 2015-05-20 | 上海应用技术学院 | Copper oxide/carbon hybrid aerogel material and its preparation method and application thereof |
| CN105885907A (en) * | 2016-05-05 | 2016-08-24 | 天津工业大学 | Preparation method for general-purpose pitch-based carbon fiber spinning pitch |
| CN107963619A (en) * | 2017-11-14 | 2018-04-27 | 石河子大学 | A kind of lightweight electromagnetic wave absorbing material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1135136C (en) | 2004-01-21 |
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