CN115924884A - Method for extracting carbon molecular sieve for methane from biogas - Google Patents
Method for extracting carbon molecular sieve for methane from biogas Download PDFInfo
- Publication number
- CN115924884A CN115924884A CN202211597367.7A CN202211597367A CN115924884A CN 115924884 A CN115924884 A CN 115924884A CN 202211597367 A CN202211597367 A CN 202211597367A CN 115924884 A CN115924884 A CN 115924884A
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- China
- Prior art keywords
- crushing
- molecular sieve
- carbon molecular
- methane
- biogas
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- 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 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 8
- 239000011280 coal tar Substances 0.000 claims abstract description 8
- 239000008107 starch Substances 0.000 claims abstract description 8
- 235000019698 starch Nutrition 0.000 claims abstract description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 8
- 239000011300 coal pitch Substances 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000005539 carbonized material Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 2
- 239000003245 coal Substances 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000000741 silica gel Substances 0.000 abstract description 2
- 229910002027 silica gel Inorganic materials 0.000 abstract description 2
- 239000010457 zeolite Substances 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000002357 osmotic agent Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002699 waste material Substances 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for extracting a carbon molecular sieve for methane from biogas, which comprises the following steps: the method comprises the following steps: thermosetting the thermosetting phenolic resin; step two: continuously crushing by a roller crusher until the crushing is more than 200 meshes; step three: adjusting the volatile content of the cured phenolic resin to 42-48% (W%); step four: then crushing to over 1200 meshes; step five: crushing at high rotation speed by a roller crusher, and mixing with coal tar, starch and coal pitch for molding. The ash content of the raw materials is less than 0.5 percent, so that the influence of impurities on the micropore adsorption effect is effectively avoided; high selectivity, and higher cost performance than activated carbon, silica gel and zeolite carbon molecular sieves; the F-type carbon molecular sieve of the invention can be used for methane purification of coal mine gas by further pore adjustment.
Description
Technical Field
A method for extracting a carbon molecular sieve for methane from biogas; the invention relates to a carbon molecular sieve and a modification method thereof; in particular to a carbon molecular sieve which covers metal ions in an inner hole to change the adsorption selectivity of the carbon molecular sieve.
Background
Municipal waste can produce a large amount of biogas during landfill treatment. The biogas is a combustible gas with a high calorific value, and comprises the main components of methane (CH 4), carbon dioxide (CO 2), a small amount of nitrogen (N2) hydrogen (H2), oxygen (O2) hydrogen sulfide (H2S) and the like. Wherein, the content of methane is 45 percent to 60 percent. Compared with other fuel gases, the methane has better anti-explosion performance and is a good clean fuel, and traditionally, methane is mostly used for heating, cooking and lighting. With the increasing of the biogas output of municipal refuse landfill sites and the continuous progress of methane purification technology in biogas, the middle-high end utilization ways of biogas are continuously expanded, and the biogas can be purified and purified by cogeneration and then be merged into natural gas pipe networks, chemical raw materials, fuel cells and the like.
The biogas purification technology mainly comprises the following steps: pressure swing adsorption separation technology (PSA), chemical absorption, physical absorption, membrane separation, and the like. The pressure swing adsorption method is the first choice in the biogas purification technology due to the advantages of no new environmental pollution, no heating and cooling energy consumption, low operation cost, flexible adjustment of methane purity, computer control of the whole process, convenient operation and the like.
The invention relates to a special adsorbent used in pressure swing adsorption technology, namely an F-type carbon molecular sieve.
Disclosure of Invention
The invention aims to provide a method for extracting a carbon molecular sieve for methane from biogas, so as to solve the problems in the background technology.
5. In order to achieve the purpose, the invention provides the following technical scheme: a method for extracting a carbon molecular sieve for methane from biogas comprises the following steps:
the method comprises the following steps: thermosetting the thermosetting phenolic resin;
step two: continuously crushing the mixture by a roller crusher until the crushing is more than 200 meshes;
step three: regulating the volatile matter of the cured phenolic resin to 42-48% (W%);
step four: then crushing to over 1200 meshes;
step five: crushing at high rotation speed by a roller crusher, and mixing with coal tar, starch and coal pitch for molding;
step six: carbonizing at 800 ℃ in a high-temperature converter under the protection of N2 to obtain a carbonized material;
step seven: modifying the carbon molecular sieve by using emulsified solutions of Ba + +, ai + + +, and Fe + +.
In the second step, the two sets of positive and negative motors drive the two sets of crushing rollers rotating in opposite directions to perform crushing in cooperation in the roller crusher.
Further, in the sixth step, the high-temperature converter performs continuous high-temperature heating by using electric heating, and the converter is opened and closed to perform jacking adjustment by using a pneumatic cylinder.
And further, in the fifth step, stirring is realized by using a crushing roller after crushing, and coal tar, starch and coal pitch are mixed and molded.
The invention has the beneficial technical effects that:
the F-type carbon molecular sieve prepared by the method has the following characteristics: (1) due to the pre-control of the raw materials, the micropore distribution of the medium hole in the product is reasonable (2), the product has high adsorption to CO2, and CH4 does not adsorb or weakly adsorbs;
1. the ash content of the raw material is less than 0.5 percent, and the influence of impurities on the micropore adsorption effect is effectively avoided;
2. high selectivity, and higher cost performance than activated carbon, silica gel and zeolite carbon molecular sieves;
4. the F-type carbon molecular sieve can be used for further pore adjustment and methane purification of coal mine gas.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for extracting a carbon molecular sieve for methane from biogas, which comprises the following steps: the method comprises the following steps:
the method comprises the following steps: thermosetting the thermosetting phenolic resin;
step two: continuously crushing by a roller crusher until the crushing is more than 200 meshes;
step three: regulating the volatile matter of the cured phenolic resin to 42-48% (W%);
step four: then crushing to over 1200 meshes;
step five: crushing at high rotation speed by a roller crusher, and mixing with coal tar, starch and coal pitch for molding;
step six: carbonizing at 800 ℃ in a high-temperature converter under the protection of N2 to obtain a carbonized material;
step seven: the carbon molecular sieve is modified by emulsified solutions of Ba + +, ai + + +, and Fe + +.
In this embodiment, in the second step, the two sets of positive and negative motors drive the two sets of crushing rollers rotating in opposite directions to perform crushing in cooperation with each other in the roller crusher.
In this embodiment, in the sixth step, the high temperature converter uses electric heating to perform continuous high temperature heating, and the converter is opened and closed to perform jacking adjustment through the pneumatic cylinder.
In this embodiment, in the fifth step, stirring is performed by a crushing roller after crushing, and the coal tar, the starch, and the coal pitch are mixed and molded.
Embodiment mode 1
Crushing solid phenolic resin (ash content is less than 0.5 percent and volatile matter is 60 percent) into 200 meshes, carrying out dry distillation treatment for 2-4 hours at 250-500 ℃ to obtain volatile matter of dry distillation powder which is 44 percent, and taking 5000g of dry distillation powder to carry out dry ball milling in an ultrafine ball mill to obtain 5000g of 1200 meshes of dry distillation powder. According to the dry distillation powder: coal tar: starch: coal tar pitch: water =100:50:5:15:30, kneading and molding the ingredients to obtain a molding material.
10000g of molding material is heated to 900 ℃ in a converter under the protection of N299.5 percent, the temperature is kept for 1 hour, and 6000g of carbonized material is obtained after the temperature is reduced.
Embodiment mode 2
Soaking 1500g of the carbonized material of example 1 in water containing 5% of Ba + +, 5% of osmotic agent, immersing thoroughly for 2-8 hours, and draining naturally. Taking the wet material to be protected by N299.9%, heating to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 1 hour, and cooling to obtain 1500g of the carbon molecular sieve, wherein the properties of the carbon molecular sieve are as follows:
| equilibrium pressure (MPa) | Amount of CO2 adsorbed | Amount of CH4 adsorbed |
| 0.1-0.6MPa | 19-45ml/gCMS | 1.0-6ml/gCMS |
Embodiment 3
1500g of the carbonized material of example 1 was soaked in a water solution containing 5% Ba + +, 5% osmotic agent 0.3% Li +, sufficiently immersed for 2 to 8 hours, and naturally drained. Taking the wet material to be protected by N299.9%, heating to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 1 hour, and cooling to obtain 1500g of the carbon molecular sieve
The properties are as follows:
| equilibrium pressure (MPa) | Amount of CO2 adsorbed | Amount of CH4 adsorbed |
| 0.1-0.6MPa | 20-55ml/gCMS | 1.0-6ml/gCMS |
Since the present invention is not limited to the above embodiments, those skilled in the art can make modifications and variations to the above embodiments without departing from the scope of the present invention.
Claims (4)
1. A method for extracting a carbon molecular sieve for methane from biogas is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: thermosetting the thermosetting phenolic resin;
step two: continuously crushing by a roller crusher until the crushing is more than 200 meshes;
step three: adjusting the volatile content of the cured phenolic resin to 42-48% (W%);
step four: then crushing to over 1200 meshes;
step five: crushing at high rotation speed by a roller crusher, and mixing with coal tar, starch and coal pitch for molding;
step six: carbonizing at 800 ℃ in a high-temperature converter under the protection of N2 to obtain a carbonized material;
step seven: the carbon molecular sieve is modified by emulsified solutions of Ba + +, ai + + +, and Fe + +.
2. The method for extracting the carbon molecular sieve for methane from the biogas as recited in claim 1, wherein the method comprises the following steps: in the second step, in the roller crusher, two sets of positive and negative motors drive two sets of crushing rollers which rotate in opposite directions to perform crushing in a matching manner.
3. The method for extracting the carbon molecular sieve for methane from the biogas as recited in claim 1, wherein the method comprises the following steps: and in the sixth step, the high-temperature converter utilizes electric heating to continuously heat at high temperature, and the converter is opened and closed to be jacked and adjusted through a pneumatic cylinder.
4. The method for extracting the carbon molecular sieve for methane from the biogas as recited in claim 1, wherein the method comprises the following steps: and in the fifth step, stirring is realized by using a crushing roller after crushing, and the coal tar, the starch and the coal pitch are mixed and molded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211597367.7A CN115924884A (en) | 2022-12-12 | 2022-12-12 | Method for extracting carbon molecular sieve for methane from biogas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211597367.7A CN115924884A (en) | 2022-12-12 | 2022-12-12 | Method for extracting carbon molecular sieve for methane from biogas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115924884A true CN115924884A (en) | 2023-04-07 |
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|---|---|---|---|
| CN202211597367.7A Pending CN115924884A (en) | 2022-12-12 | 2022-12-12 | Method for extracting carbon molecular sieve for methane from biogas |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2995495B2 (en) * | 1995-04-27 | 1999-12-27 | 日本酸素株式会社 | Carbon adsorbent, its production method, gas separation method and its apparatus |
| CN101293648A (en) * | 2008-06-06 | 2008-10-29 | 朱海良 | Technique for preparing carbon molecular sieve |
| 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 |
| CN108126660A (en) * | 2018-01-23 | 2018-06-08 | 大连理工大学盘锦产业技术研究院 | A kind of CO based on Immesion active carbon2Solid absorbent, preparation method and its usage |
-
2022
- 2022-12-12 CN CN202211597367.7A patent/CN115924884A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2995495B2 (en) * | 1995-04-27 | 1999-12-27 | 日本酸素株式会社 | Carbon adsorbent, its production method, gas separation method and its apparatus |
| CN101293648A (en) * | 2008-06-06 | 2008-10-29 | 朱海良 | Technique for preparing carbon molecular sieve |
| 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 |
| CN108126660A (en) * | 2018-01-23 | 2018-06-08 | 大连理工大学盘锦产业技术研究院 | A kind of CO based on Immesion active carbon2Solid absorbent, preparation method and its usage |
Non-Patent Citations (1)
| Title |
|---|
| 李兴伟: "变压吸附空分用酚醛树脂基炭分子筛的制备", 中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》, pages 3 * |
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