CN1303732A - Method for preparing active carbon for storing methane - Google Patents
Method for preparing active carbon for storing methane Download PDFInfo
- Publication number
- CN1303732A CN1303732A CN 00104267 CN00104267A CN1303732A CN 1303732 A CN1303732 A CN 1303732A CN 00104267 CN00104267 CN 00104267 CN 00104267 A CN00104267 A CN 00104267A CN 1303732 A CN1303732 A CN 1303732A
- Authority
- CN
- China
- Prior art keywords
- active carbon
- surface area
- specific surface
- methane
- under
- 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
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A preparation method of active carbon for storing methane includes the following steps: using petrol coke or asphalt coke as raw material, using KOH as activating agent, activating at 700-1000 deg.C for 0.5-2.0 hr. to obtain high specific surface area powdery active carbon, mixing said powdery active carbon with binding agent uniformly, and press-forming at normal temp., then making low-temp, heat-treating to obtain the formed high specific surface area active carbon. Said invention is simple in preparation process, easy to operate, short in reaction time, and the loading density of said high specific surface area active carbon can be raised, and the volume adsorption quantity for methane also can be greatly raised.
Description
The invention belongs to a kind of preparation method of active form charcoal, being specifically related to a kind of is feedstock production has the active form charcoal of high absorption storage volume to methane method with petroleum coke or pitch coke.
Natural gas is subjected to the generally attention of automobile industry just day by day as a kind of aboundresources, oligosaprobic alternative motor fuels.Yet compare with liquid fuel, the volume energy density of natural gas is low, 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.As in the CNG gas cylinder, adding adsorbent, make natural gas storage density and high pressure (CNG) under the lower pressure suitable, so just can overcome the deficiency of CNG, absorption natural gas-storing (ANG) technology that Here it is.No matter the ANG technology for the popularizing of gas-fueled vehicles, all has important use value the allotment of peak value when still using for the town gas that with the natural gas is main fuel.Selecting the suitable adsorbent with high methane adsorption capacity and adsorption desorption speed is the step that absorbed natural gas technological direction practical large-scale is used most critical.In general adsorbent, active carbon is to adsorption 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 active carbon is because the low (1200m of specific area
2About/g), pore size distribution is 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 active carbon specific area, the adsorbance of methane also is the trend of increase.Therefore the active carbon with high specific surface area of micropore prosperity might be the good material that natural gas absorption stores.
Advantages such as it is big that active carbon with high specific surface area has the BET specific area, and micropore distributes and concentrates, and the adsorption desorption performance is good.But because the active carbon with high specific surface area that makes with the KOH activation method mostly is Powdered greatly, loading density is smaller, though bigger to the quality adsorption of methane, the volume adsorption that is scaled under the standard state is then less relatively, can not satisfy requirement of actual application.
Therefore, people attempt to improve the loading density of active carbon to increase its volume adsorption capacity to methane by the whole bag of tricks.For example: Chinese patent (application number: after 98126462.X) employing petroleum coke or pitch coke abrasive dust, screening, dry back make the high-specific surface area powdered activated carbon with KOH with 1: 1～1: 6 (weight ratio) chemical activation method, be that the bonding agent utilization is carried out charing 50～150 ℃ of hot-forming backs at 700～1000 ℃, activation processing makes high-specific surface area active form charcoal with phenolic resins, coal tar pitch, coal tar.But this kind method is owing to adopt pressure sintering during moulding, and also needs after the moulding to carry out pyrocarbon, activation processing once more, so preparation technology is comparatively loaded down with trivial details, required time is long, the power consumption height.
The objective of the invention is to develop a kind of both guaranteed methane volume absorption storage volume height and method simple, the preparation method of the high-specific surface area active form charcoal that required time is short, power consumption is low.
Preparation method of the present invention is to be raw material with petroleum coke or pitch coke, with KOH is activator, make the high-specific surface area powdered activated carbon at 700～1000 ℃ of activation 0.5～2.0hr, compression moulding at normal temperatures after again this powdered activated carbon and binding agent being mixed is carried out Low Temperature Heat Treatment again and is obtained the moulding active carbon with high specific surface area.
Preparation method of the present invention is as follows:
(1) petroleum coke or pitch coke ground, sieve, dry back mixes with the ratio dipping of 1: 1～1: 6 (weight ratio) with KOH, under nitrogen protection, activates the active carbon with high specific surface area that 0.5～2.0hr makes powdery under 700～1000 ℃ then;
(2) bonding agent is dissolved in is made into pasty liquid in the solvent, add the powdered activated carbon that makes and binding agent in the pasty liquid with the ratio of 1: 0.07～1: 0.25 (weight ratio) and mix, compression moulding under 70-200MPa pressure obtains block charcoal;
(3) the block charcoal of compression moulding heating rate with 0.5～5.0 ℃/min under inert gas shielding rises to 200 ℃, and constant temperature heat-treated in 0.5～1 hour, makes product.
Aforesaid binding agent is contract methylcellulose, polyvinyl butyral resin.
Adopt the forming method that adds bonding agent, improved the loading density of active carbon with high specific surface area, thereby improved its volume adsorption greatly methane.The type charcoal that this method makes its volume adsorption to methane under 3.4MPa is 140～160v/v, and its volume adsorption to methane is 190～240v/v under 5.4MPa.
The present invention compared with prior art has following advantage:
(1) preparation technology is simple, and is easy to operate.
(2) required time is short, and it is low to consume energy, and manufacturing cost descends.
(3) improved the loading density of active carbon with high specific surface area, improved adsorbance greatly the methane volume.
Embodiments of the invention are as follows:
Embodiment 1
Get 40 gram petroleum cokes; mix with 160 gram KOH dippings; activate 1hr down at 800 ℃; make the powdery active carbon with high specific surface area; get the 0.25g methylcellulose that contracts and add the water-soluble back of separating of 2.2ml and add and stir after powdery high-specific surface area active powder charcoal 2.5 grams that make mix, compression moulding under 100MPa pressure, then under nitrogen protection in 200 ℃ of heat treatments 1 hour; make high-specific surface area active form charcoal, its BET specific area is 2308m
2/ g.This kind type charcoal volume adsorption for methane under 25 ℃, 3.4MPa is 160V/V; 5.4MPa the volume adsorption for methane is 240V/V down.
Embodiment 2
Get 40 gram petroleum cokes; mix with 40 gram KOH dippings; activate 0.7hr down at 950 ℃; make the powdery active carbon with high specific surface area, get the 0.375g methylcellulose that contracts and add that 2.5ml is water-soluble to be separated, add to stir after powdery high-specific surface area active powder charcoal 2.5 grams that make mix; compression moulding under 110MPa pressure; then under nitrogen protection in 200 ℃ of heat treatments 1 hour, make high-specific surface area active form charcoal, its BET specific area is 2000m
2/ g.This kind type charcoal volume adsorption for methane under 25 ℃, 3.4MPa is 150V/V; 5.4MPa the volume adsorption for methane is 220V/V down.
Embodiment 3
Get 40 gram petroleum cokes; mix with 80 gram KOH dippings; activate 1hr down at 900 ℃; make the powdery active carbon with high specific surface area, get the 0.5g methylcellulose that contracts and add that 3ml is water-soluble to be separated, add to stir after powdery high-specific surface area active powder charcoal 2.5 grams that make mix; compression moulding under 120MPa pressure; then under nitrogen protection in 200 ℃ of heat treatments 1 hour, make high-specific surface area active form charcoal, its BET specific area is 1800m
2/ g.This kind type charcoal volume adsorption for methane under 25 ℃, 3.4MPa is 140V/V; 5.4MPa the volume adsorption for methane is 190V/V down.
Embodiment 4
Get 40 gram petroleum cokes; mix with 200 gram KOH dippings; activate 2hr down at 750 ℃; make the powdery active carbon with high specific surface area, get the 0.175g polyvinyl butyral resin and add the dissolving of 3ml ethanol, stir after powdery high-specific surface area active powder charcoal 2.5 grams that adding makes mix; compression moulding under 140MPa pressure; then under nitrogen protection in 200 ℃ of heat treatments 1 hour, make high-specific surface area active form charcoal, its BET specific area is 1910m
2/ g.This kind type charcoal volume adsorption for methane under 25 ℃, 3.4MPa is 155V/V; 5.4MPa the volume adsorption for methane is 205V/V down.
Embodiment 5
Get 40 gram petroleum cokes; mix with 240 gram KOH dippings; activate 1.5hr down at 750 ℃; make the powdery active carbon with high specific surface area, get the 0.375g polyvinyl butyral resin and add the dissolving of 3ml ethanol, stir after powdery high-specific surface area active powder charcoal 2.5 grams that adding makes mix; compression moulding under 160MPa pressure; then under nitrogen protection in 200 ℃ of heat treatments 1 hour, make high-specific surface area active form charcoal, its BET specific area is 1600m
2/ g.This kind type charcoal volume adsorption for methane under 25 ℃, 3.4MPa is 145V/V; 5.4MPa the volume adsorption for methane is 185V/V down.
Embodiment 6
Get 30 gram pitch cokes; mix with 120 gram KOH dippings; activate 1.5 hours down in 800 ℃; make the powdery active carbon with high specific surface area, get the 0.25g methylcellulose that contracts and add that 2.2ml is water-soluble to be separated, add to stir after above-mentioned powdery high-specific surface area active powder charcoal 2.5 grams mix; compression moulding under 200MPa pressure; then under nitrogen protection in 200 ℃ of heat treatments 1 hour, make high-specific surface area active form charcoal, its BET specific area is 2100m
2/ g.This kind type charcoal volume adsorption for methane under 25 ℃, 3.4MPa is 156V/V; 5.4MPa the volume adsorption for methane is 230V/V down.
Claims (2)
1. preparation method of active carbon that is used for storing methane is characterized in that the preparation method is as follows:
(1) petroleum coke or pitch coke ground, sieve, dry back and KOH be that 1: 1～1: 6 ratio dipping mixes by weight, under nitrogen protection, activates the active carbon with high specific surface area that 0.5～2.0hr makes powdery under 700～1000 ℃ then;
(2) bonding agent is dissolved in is made into pasty liquid in the solvent, is the powdered activated carbon that makes and binding agent that 1: 0.07～1: 0.25 ratio adds in the pasty liquid and mixes by weight, and compression moulding under 70～200MPa pressure obtains block charcoal;
(3) the block charcoal of compression moulding heating rate with 0.5～5.0 ℃/min under inert gas shielding rises to 200 ℃, and constant temperature heat-treated in 0.5～1 hour, makes product.
2. method according to claim 1 is characterized in that described binding agent is contract methylcellulose, polyvinyl butyral resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00104267 CN1114481C (en) | 2000-05-11 | 2000-05-11 | Method for preparing active carbon for storing methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00104267 CN1114481C (en) | 2000-05-11 | 2000-05-11 | Method for preparing active carbon for storing methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1303732A true CN1303732A (en) | 2001-07-18 |
| CN1114481C CN1114481C (en) | 2003-07-16 |
Family
ID=4577252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00104267 Expired - Fee Related CN1114481C (en) | 2000-05-11 | 2000-05-11 | Method for preparing active carbon for storing methane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1114481C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1325154C (en) * | 2004-04-09 | 2007-07-11 | 李韬 | Production, re-activating method and products of active golden carbon |
| CN1330567C (en) * | 2003-02-17 | 2007-08-08 | 沈钟燮 | Manufacturing method of activated carbon structure having a frame |
| CN100404124C (en) * | 2004-11-02 | 2008-07-23 | 石油大学(北京) | Method for producing natural gas-storing charcoal blocky absorbent |
| CN100486686C (en) * | 2006-01-18 | 2009-05-13 | 中国科学院化学研究所 | High molecular derivatives composite material used for absorbing and storing methane, and its preparing method |
| CN102580679A (en) * | 2012-01-13 | 2012-07-18 | 昆明理工大学 | Method for preparing modified microwave activated carbon sorbent |
| CN105293491A (en) * | 2015-12-01 | 2016-02-03 | 浙江大学 | KOH solid activated active carbon preparation and forming method |
| CN106660009A (en) * | 2014-08-23 | 2017-05-10 | 恩特格里斯公司 | Microporous carbon adsorbent from natural carbohydrates |
| CN107683254A (en) * | 2015-06-18 | 2018-02-09 | 关西热化学株式会社 | Active carbon forming body and preparation method thereof and the sorbing material and storage material for having used the active carbon forming body |
| CN108516547A (en) * | 2018-05-16 | 2018-09-11 | 辽宁科技大学 | The preparation method of carbon black-coal tar pitch complex spherical activated carbon |
| CN112705167A (en) * | 2020-11-11 | 2021-04-27 | 北京飞燕石化环保科技发展有限公司 | Preparation method of MOF (Metal organic framework) modified activated carbon brick and application of MOF modified activated carbon brick in large-air-volume air filtration |
| CN113120903A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Activated carbon and preparation method and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942181B (en) * | 2012-12-04 | 2014-07-02 | 南京大学 | Preparation method of formed carbon-based material |
| CN103537260B (en) * | 2013-10-29 | 2015-07-29 | 中南大学 | Hydrophilic active carbon that a kind of sodium acetate is modified and preparation method thereof |
-
2000
- 2000-05-11 CN CN 00104267 patent/CN1114481C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330567C (en) * | 2003-02-17 | 2007-08-08 | 沈钟燮 | Manufacturing method of activated carbon structure having a frame |
| 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 |
| CN100404124C (en) * | 2004-11-02 | 2008-07-23 | 石油大学(北京) | Method for producing natural gas-storing charcoal blocky absorbent |
| CN100486686C (en) * | 2006-01-18 | 2009-05-13 | 中国科学院化学研究所 | High molecular derivatives composite material used for absorbing and storing methane, and its preparing method |
| CN102580679A (en) * | 2012-01-13 | 2012-07-18 | 昆明理工大学 | Method for preparing modified microwave activated carbon sorbent |
| CN102580679B (en) * | 2012-01-13 | 2016-01-20 | 昆明理工大学 | A kind of preparation method of modified microwave activated carbon sorbent |
| CN106660009A (en) * | 2014-08-23 | 2017-05-10 | 恩特格里斯公司 | Microporous carbon adsorbent from natural carbohydrates |
| US10335763B2 (en) | 2014-08-23 | 2019-07-02 | Entegris, Inc. | Microporous carbon monoliths from natural carbohydrates |
| CN107683254A (en) * | 2015-06-18 | 2018-02-09 | 关西热化学株式会社 | Active carbon forming body and preparation method thereof and the sorbing material and storage material for having used the active carbon forming body |
| CN105293491A (en) * | 2015-12-01 | 2016-02-03 | 浙江大学 | KOH solid activated active carbon preparation and forming method |
| CN105293491B (en) * | 2015-12-01 | 2017-09-29 | 浙江大学 | A kind of activated carbon of KOH solids activation is prepared and forming method |
| CN108516547A (en) * | 2018-05-16 | 2018-09-11 | 辽宁科技大学 | The preparation method of carbon black-coal tar pitch complex spherical activated carbon |
| CN113120903A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Activated carbon and preparation method and application thereof |
| CN113120903B (en) * | 2019-12-31 | 2023-01-10 | 中国石油化工股份有限公司 | Activated carbon and preparation method and application thereof |
| CN112705167A (en) * | 2020-11-11 | 2021-04-27 | 北京飞燕石化环保科技发展有限公司 | Preparation method of MOF (Metal organic framework) modified activated carbon brick and application of MOF modified activated carbon brick in large-air-volume air filtration |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1114481C (en) | 2003-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1114481C (en) | Method for preparing active carbon for storing methane | |
| US8691177B2 (en) | High surface area carbon and process for its production | |
| CN105148843A (en) | Active carbon granule, preparing method thereof and carbon tank | |
| CN101376114B (en) | Method for preparing metal or metallic oxide/carbon composite material | |
| CN101780954A (en) | Carbon material with high surface activity and preparation method thereof | |
| CN113299484B (en) | Preparation method of CCO/CoNiMn-LDH composite material and application of CCO/CoNiMn-LDH composite material in super capacitor | |
| CN1091073C (en) | Preparation of active carbon adsorbing and storing methane | |
| KR20090022040A (en) | Preparation of high porous activated carbon for methane storage | |
| CN113731460A (en) | N-P modified acetylene hydrochlorination non-noble metal catalyst and preparation method and application thereof | |
| CN1411903A (en) | Micropore carbon adsorbent for storing natural gas and its preparation method | |
| CN112521353A (en) | Method for preparing 2, 5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
| CN114377668A (en) | Adsorption dearsenification catalyst and preparation method thereof | |
| CN114433163A (en) | In-situ modified and pore-controllable biochar-supported ruthenium catalyst, preparation method thereof and application thereof in lignin | |
| CN113735614B (en) | Preparation method of spherical alumina | |
| CN110129084B (en) | Biomass hydrogen supply-catalytic liquefaction coupling method and supported biomass liquefaction catalyst | |
| CN113117691A (en) | Application of cobalt-based catalyst in Fischer-Tropsch synthesis reaction | |
| Ekeoma et al. | Modified coconut shell as active heterogeneous catalyst for the transesterification of waste cooking oil | |
| CN111392707B (en) | Method for preparing mesocarbon microbeads by direct coal liquefaction | |
| CN115445592B (en) | Preparation method of aluminum sol for continuous reforming catalyst | |
| CN117884148B (en) | Efficient catalyst for biodiesel and preparation method thereof | |
| CN1204046C (en) | High density high specific surface active carbon preparing method | |
| CN110028067B (en) | Super-capacitor activated carbon and preparation method thereof | |
| CN111530423B (en) | Integrally-formed granular carbon adsorbent and preparation method and application thereof | |
| KR102522123B1 (en) | Method of manufacturing activated carbon having high meso pore volume and specific surface area and activated carbon produced using the same | |
| JP2002308614A (en) | Powdery activated carbon, production method therefor and electric double layer capacitor using the activated carbon |
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 |