CN101249956A - Preparation technique of carbon-based material having energy-storage property - Google Patents
Preparation technique of carbon-based material having energy-storage property Download PDFInfo
- Publication number
- CN101249956A CN101249956A CNA2008100011208A CN200810001120A CN101249956A CN 101249956 A CN101249956 A CN 101249956A CN A2008100011208 A CNA2008100011208 A CN A2008100011208A CN 200810001120 A CN200810001120 A CN 200810001120A CN 101249956 A CN101249956 A CN 101249956A
- Authority
- CN
- China
- Prior art keywords
- energy
- carbon
- based material
- preparation technique
- storage property
- 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
Images
Abstract
A process for preparing carbon material with the property of energy storage is a method of high-temperature strong base activation, which takes petroleum pitch coke as raw material and is composed of processes of crushing and grinding, screening, charring, catalyzing and activating, washing, drying and alkali recovery. The energy storage carbon material can be mass-produced and has specific surface area of 2500-4000m2g, iodine sorption value 2500-3500mg/g, methylene blue value of 600-1200mg/g, ash less than 1%, nano microporous aperture of 0.75-1.5mm and micro volume rate larger than 90-95%. The process particularly meets the absorption and storage requirements, thereby facilitating the wide and safe application of natural gas.
Description
Affiliated technical field
The invention belongs to a kind of preparation technique of carbon-based material with storge quality, is raw material with petroleum pitch Jiao, shell carbonized material, ature of coal carbonized material, adopts high temperature highly basic chemical activation method to prepare to have high-specific surface area, nanometer level microporous energy storage carbonaceous material.By the prosperity of the produced energy storage carbonaceous material of this technology microvoid structure, the suitable especially material of doing Sweet natural gas (methane) absorption storage and high-energy accumulate electrical condenser.
Background technology
The energy strategy adjustment of national Tenth Five-Year Plan Period is mainly reflected in promoting the use of Sweet natural gas." smooth implementation of West-east Gas engineering is intended to promote " with gas for oil ", " with the gas generating ", " city gasification ".Along with the decline of prospective oil, people need seek a kind of New-type fuel that can replace oil, and Sweet natural gas reserves in the world are very abundant, verified workable reserves 147 tcms, are a kind of ideal New-type fuels.The major ingredient of Sweet natural gas is that methane accounts for 85～95%, and the energy storage carbonaceous material is an extensive indispensable novel energy-storing material of promoting Sweet natural gas.
Carbonaceous material has energy-storage property and is based on it and has abundant nanometer level microporous system, and its adsorption energy-storing effect overwhelming majority is carried out in micropore, and adsorptive capacity is subjected to micropore diameter and quantity decision.Domestic research report to senior gac is more, and technology is also comparatively ripe, and common report is used for the super-activated carbon that Gas Phase Adsorption stores, and its BET specific surface area is greater than 2000m
2/ g, iodine suction value is greater than 2000mg/g, and methylene blue number is greater than 300mg/g, and micropore size is generally 2nm～50nm, and the dynamic adsorption aperture of Sweet natural gas (methane) is 0.75～1.5nm, and super-activated carbon does not just meet the power aperture requirement of absorption natural gas-storing (methane) like this.This invention is can produce in batches to have specific surface area up to 2500～4000m
2/ g, iodine suction value is greater than 2300mg/g, the methylene blue value is greater than 600mg/g, nanometer level microporous footpath is the carbonaceous material of 0.75～1.5nm, and micropore accounts for 90～95%. of total hole volume, and this carbonaceous material meets the power aperture requirement of absorption natural gas-storing (methane), and the very suitable Sweet natural gas (methane) of doing stores (CNG) by high pressure compressed and transfers absorption to and store (ANG), is beneficial to the energy storage carbonaceous material that the safety of Sweet natural gas (methane) is applied.
Summary of the invention
The objective of the invention is to widely popularize the application of new forms of energy Sweet natural gas (methane) in order to adapt to the national energy strategical reajustment.For making the Sweet natural gas better application in the national economy every field, must change the multistage high pressure compressed storing method of Sweet natural gas (CNG) and be absorption storing method (ANG), could solve multistage high pressure compressed method and bring the factor that is absolutely unsafe of storage, and the absorption storing method need have the carbonaceous material of high-specific surface area and nano micropore structure capable, the method of suitability for industrialized production super-activated carbon is the water vapour physical activation method at present, can not produce the carbonaceous material of suitable absorption natural gas-storing, this invention is used high temperature highly basic chemical activation method for this reason, and a kind of technology of producing the carbonaceous material with high-specific surface area and nano micropore structure capable in batches is provided.
Technical scheme of the present invention is to adopt high temperature highly basic chemical activation method, is raw material with petroleum pitch Jiao, forms through broken mill, screening, dipping, charing, catalytic activation, washing, drying and alkali recovery process.Use KOH: NaOH for alkaline catalysts in reactor to flood raw material 2 hour at 75: 25 during dipping, wherein alkaline catalysts: raw material is 6: 1; The activation temperature of catalytic activation and time carry out according to the following steps, are warming up to 400 ℃～450 ℃ constant temperature 30min, are warming up to 700 ℃～750 ℃ constant temperature 30min again, be warming up to 950 ℃～1000 ℃ constant temperature 90min at last after, be cooled to room temperature and come out of the stove; The whole process of charing, catalytic activation all is to carry out under protection of nitrogen gas; With alkaliferous carbonaceous material wash, pickling is to neutral; Washing, alkaline solution after the pickling are made old liquid through electric heating reacting kettle, and detectable level then is supplemented to it and changes down batch production cycle after content reaches 60% over to and reuse, and reduces preparation cost, avoids environmental pollution, the purpose of realization alkali recycling use.
Detailed process of the present invention is as follows:
1, raw material and characteristic thereof are selected
With petroleum pitch Jiao (oil by product) is raw material, main because it is by long-chain fat hydrocarbon polycondensate, condensed-nuclei aromatics, and a small amount of low molecule organic matter is formed, and is a kind of graphited carbon element form in essence, is the black heaped-up, can not dissolve.Its quality is formed normally; Fugitive constituent 10%～15%, ash be low to moderate 1% with interior, sulphur about 2%, fixed carbon about 85%, other about 0.01%.
2, the preparation before the carbonization-activation
With the burnt fragmentation of petroleum pitch, abrasive dust, screening, getting the 100-160 order is standby raw material.
The main process of the burnt priming reaction of KOH and petroleum pitch:
KOH+C→K
2CO
3+K
2O+H
2
K
2CO
3, K
2O and graphite microcrystal and graphite microcrystal group's etching process forms netted complicated microlitic structure, and is interconnected with cross-link bond between crystallite, forms the flourishing hole with different apertures in the space.Surpass 762 ℃ of the boiling points of potassium metal K when activation temperature after, the potassium metal steam of generation will pass through the graphite six-ring, make layer and the graphite of interlayer stays hole, so potassium steam equally also can be brought into play the effect of perforate, pore-creating and reaming.
The present invention has strong absorption property for making carbon material adsorbing material at Sweet natural gas (methane), microvoid structure to carbonaceous material is implemented modulation, catalyst levels is the principal element that influences the carbonaceous material microvoid structure, is the main means of adjusting the carbonaceous material micropore diameter by the consumption that changes catalyzer KOH.
The KOH consumption is big more big more to the graphited microlitic structure destructive of carbonaceous material degree, and the carbonaceous material absorption property is good more, and it is big to prepare energy storage carbonaceous material specific surface area with KOH, flourishing relatively more than 90% of total pore volume, the less 0.87nm of mean pore size of accounting for of micropore.
By experiment with the standby raw material of KOH/ in the ratio of setting 6: 1, with KOH with the water purification dissolving again with among the burnt dipping of petroleum pitch, time 2h carries out charing, activation then, can obtain the micropore of suitable absorption natural gas-storing (methane).
The carbonaceous material that absorption stores not only will have flourishing micropore, also certain mesopore to be arranged simultaneously, be convenient to be adsorbed the conveying of matter, draw by experiment and select for use catalyst n aOH living fossil oily bitumen Jiao to help producing mesopore, two kinds of catalyst by proportion are mixed use, the effectively micropore of modulation carbonaceous material, mesopore ratio.Obtain KOH by experiment: the NaOH ratio is 75: 25, and obtaining iodine suction value is 1350mg/g, specific surface area 1530m
2/ g, total pore volume is 0.58307m
3/ g, micropore holds 0.52m
3/ g, mean pore size is 0.9nm, meets the requirement in absorption natural gas-storing (methane) power aperture.
3, carbonization-activation
Soak time is another important step among the preparation technology with the activation temperature.Catalyzer based on KOH makes petroleum pitch Jiao's microlitic structure away from greying, successively to the burnt graphite microcrystal of petroleum pitch edge-CH3 ,-CH2 ,-the CH organic carbon carries out a series of abundant activation, generating then has the baroque random carbon of certain space and forms a lot of micropores; The K that KOH and priming reaction generate
2CO
3And K
2O will be further forms etching and generates the hole in different apertures single graphite microcrystal or crystallite group; The micro-molecular gas that reaction generates in the reactivation process, CO, CO
2, H
2, H
2O, H
2S etc., in the overflow process of existing duct, Yin Gaowen expands and plays the effect of reaming, also has the potassium metal steam that generates after 762 ℃ will enter graphite layers, performance pore-creating, perforate and reaming effect.
Draw by experiment: will be in the burnt taking-up of two hours petroleum pitch of catalyst soakage, put in the special activation furnace, by the electronic intelligence sequence control system, disposable input temp and time ratio program, be warming up to 400 ℃～450 ℃ constant temperature 30min, be warming up to 700 ℃～750 ℃ constant temperature 30min again, be warming up to 950 ℃～1000 ℃ constant temperature 90min at last after, be cooled to room temperature and come out of the stove.Can prepare that to have high-specific surface area be 2500～4000m
2/ g, nanometer level microporous footpath is between 0.75～1.5nm, and micropore volume accounts for the senior gac of total pore volume 90～95%, the power aperture requirement of optimum Sweet natural gas (methane) molecule.
In the process of carbonization-activation, have potassium metal steam and overflow, potassium metal steam is very active, directly enters air and can produce blast, is the generation of avoiding exploding, and will feed nitrogen in the process of carbonization-activation, stops potassium metal steam to contact N with the direct of air
2Protection finishes to come out of the stove up to activation.
4, washing and drying
Carbonaceous material alkalinity after coming out of the stove is bigger, needs to be washed to neutrality through overpickling.By the drying machine drying, make finished product at last.
5, alkali recovery process
Set KOH according to production technique: charcoal is 6: 1, it is diluted dipping, again can lingering section after charing, activation KOH on the carbonaceous material surface, must wash this after product is come out of the stove, pickling is to neutral, can produce the pollution that alkali waste water causes environment in washing process.
The circulation that alkali is reclaimed now re-uses, and with rinsing solution suction recovery tower, changes the reacting by heating still again over to, make old liquid by electrically heated, detectable level then is supplemented to it and changes down batch production cycle after content reaches 60% over to and reuse, reduce production costs, avoid environmental pollution.
The invention has the beneficial effects as follows to produce in batches and have the energy storage carbonaceous material that suitable absorption natural gas-storing (methane) molecule power aperture requires.Can make specific surface area up to 2500～4000m2/g according to this technology, iodine suction value is greater than 2300mg/g, the methylene blue value is greater than 600mg/g, and the nanometer level microporous footpath 0.75～1.5nm that is suitable for adsorbing natural gas-storing (methane) accounts for the energy storage carbonaceous material of total pore volume 90～95%.
Description of drawings
Below in conjunction with drawings and Examples the present invention is done further to describe
Fig. 1 is the influence of catalyzer KOH consumption to pore volume and aperture
Fig. 2 is catalyzer KOH, the NaOH proportioning influence to pore volume and aperture
Fig. 3 is a process flow sheet of the present invention
Embodiment
Embodiment 1
Get the burnt abrasive dust to 100 of petroleum pitch～160um, with (KOH: NaOH is 75: 25): charcoal is 6: 1, dipping 2h, go to time and temperature variation program that activation furnace is set through the disposable input of electronic intelligence programmed controller, undertaken by following intensification, constant temperature step: 750 ℃～770 ℃/30min, 800 ℃～850 ℃/the 30min that heats up then, after be warming up to 870 ℃/30min again, at N
2Protection activation is down come out of the stove, and fully is washed to neutrality, obtains specific surface area 3887m
2/ g, iodine suction value 3750mg/g, the methylene blue value is 750mg/g, and nanometer level microporous footpath is 0.5～1.82nm, and micropore volume accounts for total hole volume 80～90%.
Embodiment 2
Get the burnt abrasive dust to 100 of petroleum pitch～120um, with (KOH: NaOH is 60: 40): charcoal is 5: 1, floods 2h, change and undertaken by following intensification, constant temperature step: 770 ℃/30min as activation furnace, 820 ℃/the 30min that heats up then, after be warming up to 870 ℃/30min again, at N
2Protection activation is down come out of the stove, and fully is washed to neutrality, obtains specific surface area 3578m
2/ g, iodine suction value 3350mg/g, the methylene blue value is 550mg/g, and nanometer level microporous footpath is 1～1.92nm, and micropore volume accounts for total hole volume 75～85%, to the adsorptive capacity of the methane effect inferior to experiment 1.
Detect
Pore structure, specific surface area adopt 1800 absorption instrument to press the BET method and measure
Iodine suction value adopts GB/7702.1-1997 to measure
The methylene blue value adopts GB/7702.22-1997 to measure.
Claims (7)
1. the preparation technique of carbon-based material that has energy-storage property is that to change present water vapour physical activation method be high temperature highly basic chemical activation method, it is characterized in that with petroleum pitch Jiao be raw material, has specific surface area 2500～4000m through breaking mill, screening, dipping, charing, catalytic activation, washing, drying and alkali recovery process composition, can producing in batches
2/ g, iodine sorption value 2500～3500mg/g, methylene blue value 600～1200mg/g, ash is less than 1%, nanometer level microporous footpath 0.75～1.5nm, and the micropore volume rate is greater than 90～95% energy storage carbonaceous material, the widespread use of Sweet natural gas safety is convenient in the requirement of attracting deposit of suitable especially Sweet natural gas (methane).
2. the preparation technique of carbon-based material with energy-storage property according to claim 1 is characterized in that: dipping is to flood raw material 2 hours in reactor with alkaline catalysts, wherein alkaline catalysts: raw material is 6: 1.
3. alkaline catalysts according to claim 2 is KOH: NaOH is 75: 25.
4. according to the said preparation technique of carbon-based material of claim 1 with energy-storage property, it is characterized in that: the activation temperature of catalytic activation and time carry out according to the following steps, be warming up to 400 ℃～450 ℃ constant temperature 30min, be warming up to 700 ℃～750 ℃ constant temperature 30min again, after being warming up to 950 ℃～1000 ℃ constant temperature 90min at last, being cooled to room temperature and coming out of the stove.
5. according to the described preparation technique of carbon-based material with energy-storage property of claim 1, it is characterized in that: the whole process of charing, catalytic activation all is to carry out under protection of nitrogen gas.
6. according to the described preparation technique of carbon-based material of claim 1, it is characterized in that with energy-storage property: washing be with alkaliferous carbonaceous material wash, pickling is to neutral.
7. according to the described preparation technique of carbon-based material of claim 1 with energy-storage property, it is characterized in that: will wash, the alkaline solution after the pickling makes old liquid through electric heating reacting kettle, detectable level then is supplemented to it and changes down batch production cycle after content reaches 60% over to and reuse.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100011208A CN101249956B (en) | 2007-07-09 | 2008-05-08 | Preparation technique of carbon-based material having energy-storage property |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710024890.X | 2007-07-09 | ||
| CN200710024890 | 2007-07-09 | ||
| CN2008100011208A CN101249956B (en) | 2007-07-09 | 2008-05-08 | Preparation technique of carbon-based material having energy-storage property |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101249956A true CN101249956A (en) | 2008-08-27 |
| CN101249956B CN101249956B (en) | 2011-04-27 |
Family
ID=39953580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100011208A Expired - Fee Related CN101249956B (en) | 2007-07-09 | 2008-05-08 | Preparation technique of carbon-based material having energy-storage property |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101249956B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973542A (en) * | 2010-11-26 | 2011-02-16 | 深圳市今朝时代新能源技术有限公司 | Preparation method of porous carbon material for supercapacitor |
| CN103827028A (en) * | 2011-09-28 | 2014-05-28 | 康宁股份有限公司 | Method for making alkali activated carbon |
| CN109999751A (en) * | 2012-07-26 | 2019-07-12 | 关西热化学株式会社 | Active carbon with high activity surface product |
| CN110461767A (en) * | 2017-03-31 | 2019-11-15 | 株式会社安德如 | The manufacturing method of active carbon |
| CN111377444A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Petroleum coke-based activated carbon and preparation method thereof |
| CN111530440A (en) * | 2020-05-07 | 2020-08-14 | 中国矿业大学 | Preparation method of coal-based porous material |
| CN111606328A (en) * | 2020-06-28 | 2020-09-01 | 中国石油化工股份有限公司 | Preparation method of energy storage carbon material, supercapacitor and energy storage carbon material |
| CN117263180A (en) * | 2023-10-12 | 2023-12-22 | 中国地质科学院岩溶地质研究所 | Preparation method of eucalyptus artificial forest waste branch activated carbon |
-
2008
- 2008-05-08 CN CN2008100011208A patent/CN101249956B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973542A (en) * | 2010-11-26 | 2011-02-16 | 深圳市今朝时代新能源技术有限公司 | Preparation method of porous carbon material for supercapacitor |
| CN101973542B (en) * | 2010-11-26 | 2013-06-12 | 深圳市今朝时代新能源技术有限公司 | Preparation method of porous carbon material for supercapacitor |
| CN103827028A (en) * | 2011-09-28 | 2014-05-28 | 康宁股份有限公司 | Method for making alkali activated carbon |
| CN103827028B (en) * | 2011-09-28 | 2016-08-24 | 康宁股份有限公司 | The method manufacturing basic activated carbon |
| CN109999751A (en) * | 2012-07-26 | 2019-07-12 | 关西热化学株式会社 | Active carbon with high activity surface product |
| CN110461767A (en) * | 2017-03-31 | 2019-11-15 | 株式会社安德如 | The manufacturing method of active carbon |
| CN111377444A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Petroleum coke-based activated carbon and preparation method thereof |
| CN111530440A (en) * | 2020-05-07 | 2020-08-14 | 中国矿业大学 | Preparation method of coal-based porous material |
| CN111606328A (en) * | 2020-06-28 | 2020-09-01 | 中国石油化工股份有限公司 | Preparation method of energy storage carbon material, supercapacitor and energy storage carbon material |
| CN117263180A (en) * | 2023-10-12 | 2023-12-22 | 中国地质科学院岩溶地质研究所 | Preparation method of eucalyptus artificial forest waste branch activated carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101249956B (en) | 2011-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101249956B (en) | Preparation technique of carbon-based material having energy-storage property | |
| Lee et al. | Review of the use of activated biochar for energy and environmental applications | |
| Zhou et al. | Upgrading earth-abundant biomass into three-dimensional carbon materials for energy and environmental applications | |
| Demir et al. | Lignin‐derived heteroatom‐doped porous carbons for supercapacitor and CO2 capture applications | |
| CN1843906B (en) | Method for preparing high-specific surface area active carbon by petroleum coke | |
| Jain et al. | Hydrothermal conversion of biomass waste to activated carbon with high porosity: A review | |
| Akdemir et al. | Ruthenium modified defatted spent coffee catalysts for supercapacitor and methanolysis application | |
| CN101973542B (en) | Preparation method of porous carbon material for supercapacitor | |
| Shen et al. | A facile synthesis of nitrogen-doped porous carbons from lignocellulose and protein wastes for VOCs sorption | |
| Li et al. | Preparation and characterization of activated carbon from Kraft lignin via KOH activation | |
| CN101428795B (en) | Carbon preparation material based on coke modification and sulphur-applying activated char, and production process thereof | |
| Chen et al. | Preparation of nitrogen-doped porous carbon from waste polyurethane foam by hydrothermal carbonization for H2S adsorption | |
| CN104649265A (en) | Method for preparing active carbon with high specific surface area from walnut shell | |
| Brazil et al. | Sustainable process to produce activated carbon from Kraft lignin impregnated with H3PO4 using microwave pyrolysis | |
| Bhat et al. | Supercapacitors production from waste: A new window for sustainable energy and waste management | |
| CN106423113A (en) | Preparation method of modified oil shale semicoke adsorbent | |
| Kamran et al. | Solvent-free conversion of cucumber peels to N-doped microporous carbons for efficient CO2 capture performance | |
| JP2021138562A (en) | Method for producing hydrogen | |
| CN104326470A (en) | Method for preparing high specific surface area micron-scale spherical activated carbon from carboxymethyl cellulose | |
| Tang et al. | Waste plastic to energy storage materials: a state-of-the-art review | |
| KR101995128B1 (en) | Microwave reforming apparatus for gas reforming | |
| Emrooz et al. | One-step green synthesis of meso-microporous carbons by self-activation of lemon wastes for high-performance supercapacitors | |
| Wan et al. | Thermo-catalytic conversion of waste plastics into surrogate fuels over spherical activated carbon of long-life durability | |
| CN102417835A (en) | Method for preparing hydrogen-rich gas by performing catalytic gasification on petroleum coke | |
| CN106629722A (en) | Preparation method of rice husk/coal asphalt-based porous graphitized carbon nano sheet used for supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110427 Termination date: 20130508 |