CN1283354C - Preparation method of carbon molecular sieve - Google Patents
Preparation method of carbon molecular sieve Download PDFInfo
- Publication number
- CN1283354C CN1283354C CN 02120743 CN02120743A CN1283354C CN 1283354 C CN1283354 C CN 1283354C CN 02120743 CN02120743 CN 02120743 CN 02120743 A CN02120743 A CN 02120743A CN 1283354 C CN1283354 C CN 1283354C
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- CN
- China
- Prior art keywords
- molecular sieve
- carbon molecular
- component
- preparation
- petroleum coke
- 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.)
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 35
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 49
- 230000004913 activation Effects 0.000 claims abstract description 17
- 239000002006 petroleum coke Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 14
- 239000011269 tar Substances 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000010426 asphalt Substances 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000000465 moulding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000005539 carbonized material Substances 0.000 description 3
- 241000758789 Juglans Species 0.000 description 2
- 235000009496 Juglans regia Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000020234 walnut Nutrition 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention has introduced the preparation method of a carbon molecular sieve, especially regard petroleum coke as the method for preparing the carbon molecular sieve of raw materials, pulverize petroleum coke to below 100 mesh, add binder and appropriate amount of water to knead, knead and carry on shaping treatment after being homogeneous, the shaping treatment thing is charred after drying treatment, then carry on or control the activation as required; or by a two-component pore adjustment method; or the combined aperture treatment process of the controlled activation and two-component aperture adjustment method, the carbon molecular sieve is obtained, the strength of the obtained product is more than 95 percent, the aperture width of the obtained product can be controlled within 30 AA, the minimum can be controlled within 10 AA, and the product can be used in the application fields of PSA method air separation oxygen generation and nitrogen generation, PSA method hydrogen-containing gas separation and purification hydrogen, catalysts and carriers thereof, and the like.
Description
Technical field
The present invention relates to a kind of is the method for feedstock production carbon molecular sieve with the petroleum coke.
Background technology
Carbon molecular sieve is the novel charcoal material that concentrate very much in a kind of aperture, be widely used in PSA method gas and separate purification, many aspects such as catalyst carrier, but because coal and shell are all adopted in present carbon molecular sieve manufacturing is raw material, the product aperture mainly is suitable for preparing nitrogen by separating air or system oxygen, and product strength is poor, can not satisfy the requirement of long-term operation in the actual production, and range of application is restricted.
Patent CN107029A discloses a kind of with the method for walnut shell manufacturing air separation nitrogen-enriching with carbon molecular sieve; this method is walnut shell to be placed a charing of converter under inert atmosphere; one time carbide is pulverized back adding additives moulding; after the article shaped drying in converter through the secondary charing; obtain the air separation nitrogen-enriching carbon molecular sieve after the cooling; all adopt nitrogen protection in described twice carbonization process of this method, making the process complexity has increased product cost.
Patent CN1030030A discloses the fixedly method of phase carbon molecular sieve of a kind of coal-made chromatogram, and this method is coal to be added alkali add acid treatment, makes in this handled thing and contains humic acid, and this handled thing is through repeatedly neutralizing, wash, obtaining the carbon molecular sieve product after the drying.The described process of this method need add acid treatment, adds alkali treatment or adds the alkali neutralisation treatment, and from the aforesaid operations process, operating process requires height to the anticorrosion of equipment, and exists bigger problem of environmental pollution.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with the petroleum coke, and technical process is simple, pollution is little, can be by the method for the different carbon molecular sieves of difference requirement preparation.
The present invention is achieved in that
Petroleum coke powder is broken to below 100 orders, according to petroleum coke: binding agent: water=: 60～90: 10～40: the ratio of 0～10 percentage by weight adds binding agent in petroleum coke and water is mediated, after mediating evenly this kneaded material is carried out forming processes, after handling, forming processes thing drying carries out charing, then or the control activation; Or by two component holes adjustment method; Or control activation and the aperture treatment process of adjusting the combined method of method with A, B two component holes, obtain carbon molecular sieve of the present invention.。
Adhesive recited above is meant asphalt, ethylene cracking tar or coal tar or its blending component.
Described carbonization temperature is 400 ℃～800 ℃.
Described aperture treatment process is:
(1) control activation: in activation temperature is 800 ℃～1000 ℃ scopes, be controlled at (2～15) kg/kg product according to the amount of the different activated water steam of product, or control CO
2Or the amount of air is at (0.1～3) m
3/ kg product promptly obtains carbon molecular sieve of the present invention;
(2) two component holes are adjusted method: this method is characterised in that selects A component and B component to be mixed into mixed composition, with the carbide and the blending ingredients mixing that reconciles into after the described charing processing, ask at 0.1h～24h when guaranteeing dipping absorption, to ℃ carry out drying in room temperature to 250 through the material of impregnation process then and handle 2min～200min, and carry out described charing again and handle and promptly get carbon molecular sieve;
(3) above-mentioned (1) the treatment process combination with (2) can be obtained carbon molecular sieve.
Above-mentioned (2) described A component is pitch or the tar material in oil or the chemical field, and these materials can be asphalt, clarified oil, ethylene cracking tar, coal tar, and described B component is benzene class material, diesel oil, gasoline, kerosene.
The ratio of A component and B component is: 20～80: 80～20.
The invention has the advantages that: the employing petroleum coke is a raw material, behind the oil abrasive dust, through moulding, charing and different apertures treatment process, thereby obtain the carbon molecular sieve in different apertures, products obtained therefrom intensity is more than 95%, can be controlled in 30 by products obtained therefrom of the present invention, aperture, minimum controllable is in 10 , and product can be used for PSA method air-separating oxygen-making and separates applications such as purifying hydrogen of hydrogen, catalyst and carrier thereof with system nitrogen, PSA method hydrogen-containing gas.
The specific embodiment
Further specify technical characterstic of the present invention by the following examples.
Embodiment 1
Get the petroleum coke powder 2kg of granularity below 160 orders, add ethylene cracking tar 0.4Kg, adding water 0.1Kg mediates, and mix, moulding on former, naturally dried 5 minutes, then 10min is handled in the charing under 750 ℃ of conditions of this material, material is handled in charing added activation furnace, under 950 ℃ of conditions, feed water vapour and control activation, the amount of water vapour is the 2kg/kg product, and resulting carbon molecular sieve product is in H2, N2 two component PSA technologies, and purified hydrogen concentration has reached 99.99%.
Embodiment 2
Get the following petroleum coke powder 2kg of 180 orders, (it is asphalt that the weight of this hybrid adhesive is formed: ethylene cracking tar 85: 15) mediate for adding asphalt, ethylene cracking tar hybrid adhesive 0.5kg, forming processes, molding mass adds retort under 700 ℃ of conditions, 20min is handled in charing, then carbonized material is added activation furnace, water flowing steam carries out activation processing under 900 ℃ of conditions, the amount of water vapour is controlled at the 5kg/kg product, and acquisition carbon molecular sieve product separates purified hydrogen in catalysis drying gas concentration can reach more than 92%.
Embodiment 3
Get the petroleum coke powder 2kg of granularity below 100 orders, add coal tar 0.5kg and mediate, forming processes is dried 20min with molding mass, should expect under 850 ℃, handles 5min and promptly gets carbonized material.
Get coal tar 1kg, add gasoline 0.5kg stirring and evenly mixing and make modifier, add in modifier then that carbonized material floods, absorption, time is 8h, macerate dried at 100 ℃ handle 20min and send into activation equipment and carry out activation processing with water vapour, activation temperature is 920 ℃.The activated water quantity of steam is the 6kg/kg product, and gained carbon molecular sieve product pore diameter is at 11 -40 , and the gained carbon molecular sieve can be used for removing benzene class material from air, also can be used for catalyst carrier.
Embodiment 4
Be ready to embodiment 2 gained carbon molecular sieve products standby, get ethylene cracking tar 2kg, add diesel oil component 2kg and make modifier, embodiment 2 gained carbon molecular sieves are added this modifier carry out impregnation process 6h, then macerate being carried out drying handles, this drying products therefrom is handled the carbon molecular sieve that promptly gets newly through charing, and this carbon molecular sieve is applicable to the drying processing of air separation, gas etc.
Claims (6)
1. the preparation method of carbon molecular sieve, it is characterized in that: petroleum coke powder is broken to below 100 orders, according to petroleum coke: binding agent: water=60～90: 10～40: the ratio of 0～10 percentage by weight adds binding agent in petroleum coke and water is mediated, after mediating evenly this kneaded material is carried out forming processes, after handling, forming processes thing drying carries out charing, then or the control activation; Or by two component holes adjustment method; Or control activation and the aperture treatment process of adjusting the combined method of method with A, B two component holes, obtain carbon molecular sieve of the present invention.
2. the preparation method of carbon molecular sieve according to claim 1, it is characterized in that: described carbonization temperature is 400 ℃～800 ℃.
3. the preparation method of carbon molecular sieve according to claim 1, it is characterized in that: described aperture treatment process is:
(1) control activation: under 800 ℃～1000 ℃ temperature conditions carbide is sent into activation furnace, the consumption of control water vapour is at 2～15kg product, and activated media is CO
2, air, consumption is pressed 0.1-3m
3/ kg the control of product promptly gets required charcoal molecule product;
(2) two component holes are adjusted method: this method is characterised in that selects A component and B component to be mixed into mixed composition, with the carbide and the blending ingredients mixing that reconciles into after the described charing processing, guarantee that the dipping adsorption time is at 0.1h～24h, to ℃ carry out drying in room temperature to 250 through the material of impregnation process then and handle 2min～200min, carry out described charing again and handle, promptly get carbon molecular sieve;
(3) above-mentioned (1) the treatment process combination with (2) can be obtained carbon molecular sieve.
4. the preparation method of carbon molecular sieve according to claim 1, it is characterized in that: described A component is pitch or the tar material in oil or the chemical field, these materials can be asphalt, clarified oil, ethylene cracking tar, coal tar, and described B component is benzene class material, diesel oil, gasoline, kerosene.
5. the preparation method of carbon molecular sieve according to claim 1, it is characterized in that: the ratio of A component and B component is: 20～80: 80～20.
6. the preparation method of carbon molecular sieve according to claim 1 is characterized in that: described adhesive is meant asphalt, ethylene cracking tar or coal tar or its blending component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02120743 CN1283354C (en) | 2002-05-31 | 2002-05-31 | Preparation method of carbon molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02120743 CN1283354C (en) | 2002-05-31 | 2002-05-31 | Preparation method of carbon molecular sieve |
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|---|---|
| CN1462650A CN1462650A (en) | 2003-12-24 |
| CN1283354C true CN1283354C (en) | 2006-11-08 |
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|---|---|---|---|
| CN 02120743 Expired - Fee Related CN1283354C (en) | 2002-05-31 | 2002-05-31 | Preparation method of carbon molecular sieve |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596445B (en) * | 2009-06-05 | 2011-06-08 | 安徽理工大学 | Method for preparing carbon molecular sieve adsorbent |
| CN101642701B (en) * | 2009-08-14 | 2011-12-28 | 威海华泰分子筛有限公司 | Method for preparing carbon molecular sieve by using floral foam leftover materials |
| CN102631887B (en) * | 2012-04-24 | 2014-04-30 | 安徽理工大学 | Preparation method of carbon molecular sieve adsorbent with anti-static performance |
| CN102633253B (en) * | 2012-05-04 | 2013-08-07 | 威海华泰分子筛有限公司 | Method for preparing carbon molecular sieve |
| CN104006632B (en) * | 2014-06-06 | 2015-11-18 | 湖州强马分子筛有限公司 | The environmental protection drying and processing method of carbon molecular sieve and system thereof |
| JP6906503B2 (en) * | 2015-09-30 | 2021-07-21 | ダウ グローバル テクノロジーズ エルエルシー | Carbon molecular sieve adsorbent prepared from activated carbon and useful for propylene-propane separation |
| CN108467035A (en) * | 2018-02-11 | 2018-08-31 | 安徽海德化工科技有限公司 | The preparation method of carbon molecular sieve based on petroleum coke |
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| CN1462650A (en) | 2003-12-24 |
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