CN1091073C - Preparation of active carbon adsorbing and storing methane - Google Patents
Preparation of active carbon adsorbing and storing methane Download PDFInfo
- Publication number
- CN1091073C CN1091073C CN98126462A CN98126462A CN1091073C CN 1091073 C CN1091073 C CN 1091073C CN 98126462 A CN98126462 A CN 98126462A CN 98126462 A CN98126462 A CN 98126462A CN 1091073 C CN1091073 C CN 1091073C
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- methane
- surface area
- specific surface
- carbon
- 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.)
- Expired - Fee Related
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 title claims description 27
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002006 petroleum coke Substances 0.000 claims abstract 3
- 239000011334 petroleum pitch coke Substances 0.000 claims abstract 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 18
- 239000003610 charcoal Substances 0.000 description 15
- 238000001994 activation Methods 0.000 description 7
- 238000000748 compression moulding Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 239000011295 pitch Substances 0.000 description 5
- 230000000274 adsorptive effect Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000006253 pitch coke Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a preparation method of activated carbon adsorbing and storing methane. In the method, petroleum coke or pitch coke used as raw material and a KOH activating agent are used for preparing pulverulent activated carbon with large specific surface area; the pulverulent activated carbon is mixed with adhesive by the ratio of 1:0.30 to 0.60; the mixture is formed by extrusion under the conditions of 20 to 130 DEG C and 50 to 320MPa pressure, the mixture is carbonized at 700 to 1000 DEG C, and is activated at 700 to 1000 DEG C by using water vapor or carbon dioxide, and thus, formed activated carbon with large specific surface area is prepared. The formed activated carbon prepared by the method has a methane volume adsorbing amount of 140 to 170 V/V at 26 DEG C and 3.5MPa and 190 to 240 V/V at 5.5MPa. The formed activated carbon has the advantages of simple preparation method, large methane volume adsorbing amount, etc. The present invention provides favorable prospects for large-scale application in the future.
Description
The invention belongs to a kind of preparation method of active carbon, being specifically related to a kind of is the method for the active carbon with high specific surface area of feedstock production absorbing and storing methane with refinery coke or pitch coke.
Sweet natural gas is subjected to the generally attention of automobile industry just day by day as a kind of aboundresources, the oligosaprobic automobile fuel that substitutes.Yet compare with gasoline, the energy density of Sweet natural gas (combustion heat of every volume fuel) is lower, and in order to address this problem, people have worked out compressed natural gas (CNG) technology, and have been applied to automobile industry.But (＞the safety 20MPa) brought and economic problems have limited it and have used widely and develop because high pressure.By contrast, absorbed natural gas technology (ANG) can (3-4MPa) charge into Sweet natural gas in the lightweight container that sorbent material is housed under relatively low pressure, utilizes adsorption technology to come natural gas-storing, thereby is expected to be applied in the development of automobile industry.Selecting the suitable sorbent material with high methane loading capacity and adsorption desorption speed is the step that absorbed natural gas technological direction practical large-scale is used most critical.In general sorbent material, gac is to loading capacity maximum (the Parkyns ND of methane, Quinn D F.Porosity in Carbons, ed.Patrick J W.Edward Arnold, London, 1995.PP.302), yet commercial at present ordinary granular gac is because the too low (1200m of specific surface area
2About/g), pore distribution is too wide, and the amount of absorbing and storing methane only is equivalent to 1/2nd (Quinn D F, Macdonald J A.Carbon, 1992,30 (7): 1097 of 20MPa lower compression storing methane amount under normal temperature, 3.4MPa.Under normal temperature 3-4MPa, the absorption of methane mainly is to occur in micropore, and along with the increase of gac specific surface area, the adsorptive capacity of methane also is the trend of increase.The active carbon with high specific surface area that makes with the KOH activation method mostly is Powdered greatly, packing density is smaller, though the quality adsorption to methane is bigger under normal temperature 3.5MPa, the volume adsorption that is scaled under the standard state is about 122V/V, less relatively, can not satisfy requirement of actual application.
The object of the present invention is to provide the high preparation method of active carbon of a kind of methane volume loading capacity.
Preparation method of the present invention comprises the steps:
(1) refinery coke or pitch coke are milled to 180-40 μ m, mix with the KOH solution impregnation dry back, wherein refinery coke or pitch coke and KOH weight ratio are 1: 1-6 under nitrogen protection, activates 0.5-2.0hr down at 700-1000 ℃ and makes the powdered active carbon with high specific surface area then;
(2) powdered carbon that aforesaid method is made and binding agent (weight ratio) are by 1: mixed (0.30-0.60) is even, and compression moulding under 20-130 ℃, 50-320MPa pressure obtains block charcoal;
(3) block absorbent charcoal temperature rise rate with 0.5-5.0 ℃/min under protection of nitrogen gas is risen to 700-1000 ℃ of charing processing 0.5-2 hour;
(4) with the block charcoal after the charing, under 700-1000 ℃, activate 0.5-2.0 hour with activator, can make the active carbon with high specific surface area of moulding.
Described binding agent is pitch, coal tar, resin.
Described activator is water vapour, carbonic acid gas.
The present invention has following advantage:
1. the pressed active carbon BET specific surface area of the present invention's preparation is 1916-2700m
2/ g.
2. utilize the method moulding of adding binding agent, improved the packing density of gac, thereby improved the volume adsorption of gac for methane, the volume adsorption to methane under 3.5MPa can reach 170V/V, and the methane volume adsorption under the 5.5MPa can reach 240V/V.
Embodiments of the invention are as follows:
Comparative Examples
Get 40 gram refinery cokes, mix with the KOH solution impregnation that contains 160 gram KOH, activate 1.5hr down at 800 ℃, make the powdery active carbon with high specific surface area, this powdered carbon quality adsorption for methane under 26 ℃, 3.5MPa is 0.35g/g, and the volume adsorption that is scaled under the standard state is 122V/V; 5.5MPa the volume adsorption to methane is 158V/V down.
Embodiment 1
Make the high specific area gac of powdery by the method in the Comparative Examples; Get this kind powdery carbon 3 grams, add 1.9 gram mid-temperature pitches, at 80 ℃; compression moulding under the 160MPa pressure, then under nitrogen protection in 800 ℃ of charings 1 hour, again in 800 ℃ of following steam activations 1.5 hours; make high-specific surface area active form charcoal, its BET specific surface area is 2308m
2/ g.This kind type charcoal is at 26 ℃, and the volume adsorption for methane under the 3.5MPa is 170V/V; 5.5MPa the volume adsorption for methane is 240V/V down.
Embodiment 2
Make the high-specific surface area powdered carbon by the method in the Comparative Examples; Get this kind powdery carbon 3 grams; mix with 1.8 gram mid-temperature pitches; compression moulding under 80 ℃, 160MPa pressure; then under protection of inert gas in 800 ℃ of charings 1.0 hours; again 800 ℃ of carbon dioxide activation 1.0 hours; make high-specific surface area active form charcoal, its BET specific surface area is 2053m
2/ g.This kind type charcoal adsorptive capacity for methane under 26 ℃, 3.5MPa is 160V/V; 5.5MPa the volume adsorption for methane is 218V/V down.
Embodiment 3
Make the high-specific surface area powdered carbon by the method in the Comparative Examples; Get this kind powdered carbon 2 gram, mix, compression moulding under 25 ℃, 100MPa pressure with 3 gram coal tar; then under nitrogen protection in 800 ℃ of charings 1.0 hours; at 900 ℃ of following steam activation 0.5hr, make high-specific surface area type charcoal again, its BET specific surface area is 2700m
2/ g.This kind type charcoal adsorptive capacity for methane under 26 ℃, 3.5MPa is 146V/V; 5.5MPa the adsorptive capacity for methane is 202V/V down.
Embodiment 4
Make the high-specific surface area powdered carbon by the method in the Comparative Examples; Get this kind powdery carbon 3 gram, mix, depress compression moulding down at 120 ℃, 50MPa with 1.3 gram resol.In 800 ℃ of charings 1.0 hours, and then in 800 ℃ of following steam activations 1.0 hours, obtain high-specific surface area type charcoal under nitrogen protection, its BET specific surface area is 2200m
2/ g.This kind type charcoal volume adsorption to methane under 26 ℃, 3.5MPa is 148V/V; 5.5MPa the volume adsorption to methane is 191V/V down.
Embodiment 5
Make the high-specific surface area powdered carbon by the method in the Comparative Examples; Get this kind powdery carbon 3 grams, mix with 1.9 gram mid-temperature pitches, at 83 ℃, compression moulding under the 320MPa pressure.In 800 ℃ of charings 1.0 hours, and then in 800 ℃ of following steam activations 1.0 hours, obtain high-specific surface area type charcoal under nitrogen protection, its BET specific surface area is 2016m
2/ g.This kind type charcoal volume adsorption to methane under 26 ℃, 3.5MPa is 154V/V; 5.5MP the volume adsorption with methane is 215V/V down.
Embodiment 6
Get 30 gram pitch cokes, mix, activate 1.5 hours down, make the powdery active carbon with high specific surface area in 800 ℃ with the KOH solution impregnation that contains 120 gram KOH; Get this kind powdery carbon 4 gram, add mid-temperature pitch 2.67 grams, compression moulding under 86 ℃, 160MPa pressure, then under protection of inert gas in 800 ℃ of charings 1 hour, in 800 ℃ of steam activations 1.0 hours, make the type charcoal again, its BET specific surface area is 1916m
2/ g.This kind type charcoal volume adsorption to methane under 26 ℃, 3.5MPa is 142V/V; 5.5MPa the volume adsorption to methane is 196V/V down.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98126462A CN1091073C (en) | 1998-12-25 | 1998-12-25 | Preparation of active carbon adsorbing and storing methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98126462A CN1091073C (en) | 1998-12-25 | 1998-12-25 | Preparation of active carbon adsorbing and storing methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1258638A CN1258638A (en) | 2000-07-05 |
| CN1091073C true CN1091073C (en) | 2002-09-18 |
Family
ID=5229680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98126462A Expired - Fee Related CN1091073C (en) | 1998-12-25 | 1998-12-25 | Preparation of active carbon adsorbing and storing methane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1091073C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313365C (en) * | 2003-11-07 | 2007-05-02 | 中国科学院金属研究所 | Preparation of high-specific surface area nanometer carbon tube |
| CN1325154C (en) * | 2004-04-09 | 2007-07-11 | 李韬 | Production, re-activating method and products of active golden carbon |
| CN1304281C (en) * | 2004-06-11 | 2007-03-14 | 中国科学院山西煤炭化学研究所 | Preparing method for porous carbon with high specific surface area |
| CN100337911C (en) * | 2005-01-27 | 2007-09-19 | 西北农林科技大学 | Method for producing active carbon by using straw mixed raw material |
| CN101028923B (en) * | 2006-03-03 | 2012-01-04 | 中国人民解放军63971部队 | Production of super-activated carbon from petroleum coke |
| CN101255945B (en) * | 2007-12-12 | 2010-04-21 | 北京化工大学 | A method for storing methane and removing carbon dioxide using activated carbon microsphere adsorbent |
| CN102302925B (en) * | 2011-08-23 | 2013-06-12 | 华南理工大学 | Natural gas adsorbent, adsorption tank and method for adsorption, storage and transportation using it |
| CN102897761A (en) * | 2012-09-26 | 2013-01-30 | 南京正森环保科技有限公司 | Preparation method of special activated carbon used for carbon canister of automobile or motorcycle |
| CN103721678A (en) * | 2012-10-12 | 2014-04-16 | 刘克欣 | Efficient absorbent used for purification of biogass and coalbed methane and preparation method thereof |
| CN105257980B (en) * | 2015-10-28 | 2018-04-03 | 重庆工商大学 | A kind of technical method of low pressure gas storage methane or natural gas |
| CN105731451A (en) * | 2016-02-16 | 2016-07-06 | 大连理工大学 | A modification method of petroleum coke-based activated carbon and its application |
| CN111573667B (en) * | 2020-06-28 | 2022-02-01 | 中国石油化工股份有限公司 | Energy storage carbon material, supercapacitor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064805A (en) * | 1988-10-01 | 1991-11-12 | Kansai Netsukagaku Kabushiki Kaisha | Production of high quality activated carbon |
| JPH0915711A (en) * | 1995-06-30 | 1997-01-17 | Fuji Photo Optical Co Ltd | Data imprinting device for camera |
| CN1186043A (en) * | 1996-12-24 | 1998-07-01 | 中国科学院山西煤炭化学研究所 | Method for producing activated carbon with high specific surface area from asphalt |
| JPH10199767A (en) * | 1997-01-07 | 1998-07-31 | Kansai Coke & Chem Co Ltd | Manufacturing method of carbon material for electric double layer capacitor |
-
1998
- 1998-12-25 CN CN98126462A patent/CN1091073C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064805A (en) * | 1988-10-01 | 1991-11-12 | Kansai Netsukagaku Kabushiki Kaisha | Production of high quality activated carbon |
| JPH0915711A (en) * | 1995-06-30 | 1997-01-17 | Fuji Photo Optical Co Ltd | Data imprinting device for camera |
| CN1186043A (en) * | 1996-12-24 | 1998-07-01 | 中国科学院山西煤炭化学研究所 | Method for producing activated carbon with high specific surface area from asphalt |
| JPH10199767A (en) * | 1997-01-07 | 1998-07-31 | Kansai Coke & Chem Co Ltd | Manufacturing method of carbon material for electric double layer capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1258638A (en) | 2000-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5204310A (en) | High activity, high density activated carbon | |
| US5276000A (en) | Preparation for high activity, high density carbon | |
| US5416056A (en) | Production of highly microporous activated carbon products | |
| US5304527A (en) | Preparation for high activity, high density carbon | |
| Manocha | Porous carbons | |
| CN1091073C (en) | Preparation of active carbon adsorbing and storing methane | |
| US5250491A (en) | Preparation of high activity, high density activated carbon | |
| US5238470A (en) | Emission control device | |
| EP0649815B1 (en) | Highly microporous carbons and process of manufacture | |
| US5965483A (en) | Highly microporous carbons and process of manufacture | |
| US5626637A (en) | Low pressure methane storage with highly microporous carbons | |
| US5710092A (en) | Highly microporous carbon | |
| CN105148843A (en) | Active carbon granule, preparing method thereof and carbon tank | |
| CN1411903A (en) | Micropore carbon adsorbent for storing natural gas and its preparation method | |
| JP2006213544A (en) | Granular active carbon and its manufacturing method | |
| CN1303732A (en) | Method for preparing active carbon for storing methane | |
| Wang et al. | Scalable production of wood carbon microspheres for high-efficiency carbon dioxide capture | |
| Song et al. | Preparation and applications of biomass porous carbon | |
| KR101998190B1 (en) | Method for Preparation of mesoporous activated carbon from needle coke via 2nd steam activation | |
| CN100404124C (en) | A method for manufacturing a bulk carbonaceous adsorbent for storing natural gas | |
| Li et al. | Forming Active Carbon Monoliths from H 3 PO 4-loaded Sawdust with Addition of Peanut Shell Char. | |
| KR102877555B1 (en) | Manufacturing method of active coke and active coke manufactured using the same | |
| Satish | Porous carbons | |
| Miyawaki | Pressurized physical activation method for production of high-performance activated carbons based on microdomain pore structure model | |
| Li et al. | Activated Carbon Monolith Derived from Polymer and Fast Pyrolytic Char: Effect of Bio-Oil Phenol-Formaldehyde Resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |