CN114682233B - Core-shell type carbon molecular sieve and preparation method and application thereof - Google Patents
Core-shell type carbon molecular sieve and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 87
- 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 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 53
- 239000011258 core-shell material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010410 layer Substances 0.000 claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000010000 carbonizing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000012792 core layer Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000007833 carbon precursor Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of carbon molecular sieve preparation, in particular to a core-shell carbon molecular sieve and a preparation method and application thereof, wherein the method comprises the following steps: carbonizing, activating and regulating aperture of the carbon precursor to prepare a nuclear layer carbon molecular sieve; grinding the nuclear layer carbon molecular sieve into powder for standby; preparing a shell raw material, an organic solvent and a template agent into an impregnating solution according to a proportion; and (3) immersing the powder in an impregnating solution, uniformly mixing, drying, carbonizing, removing a template agent, and drying to obtain the core-shell carbon molecular sieve. The core-shell type carbon molecular sieve is used for methane separation chromatographic columns, and can be used for preferentially adsorbing heavy components in waste gas on the shell layers of the carbon molecular sieve, so that the influence on the core layers is reduced, the pollution to the chromatographic columns is reduced, and the aging frequency and time of the chromatographic columns are reduced.
Description
Technical Field
The invention relates to the technical field of carbon molecular sieve preparation, in particular to a core-shell carbon molecular sieve and a preparation method and application thereof.
Background
In recent years, there has been an increasing concern about the environmental impact of methane gas, and when the methane content in exhaust gas reaches 5 to 15%, there is a risk of explosion, so that the methane content in exhaust gas needs to be tested. At present, the quantitative analysis of methane by using a chromatographic method is a common method, but when high-concentration recombination exists in the waste gas, the pollution of a chromatographic column can be caused, the next sample injection analysis is influenced, and the aging time and frequency of the chromatographic column are increased.
In view of this, there is a need to develop a new molecular sieve for gas chromatography that reduces column aging time and frequency.
Disclosure of Invention
The invention aims to provide a core-shell type carbon molecular sieve, a preparation method and application thereof, which are used for preferentially adsorbing heavy components in waste gas on a shell layer of the carbon molecular sieve, reducing the influence on the core layer and reducing the pollution to a chromatographic column.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the preparation method of the core-shell carbon molecular sieve comprises the following steps:
s1: carbonizing, activating and regulating the aperture of the carbon precursor to prepare a nuclear layer carbon molecular sieve with the aperture of 0.4-0.5 nm;
the carbon precursor comprises one or more of biomass, coal quality and high molecular polymer;
the pore diameter regulating material includes one or several of benzene, methane, ethane, propane and toluene.
S2: grinding the nuclear layer carbon molecular sieve in the S1 into powder with the particle size of 100-150 meshes for standby;
s3: preparing a shell raw material, an organic solvent and a template agent into an impregnating solution according to the mass ratio of 1 (2-10) to 0.5-1;
the shell raw material comprises one or more of phenolic resin, cellulose, lignin and sucrose;
the organic solvent comprises one or more of ethanol, dimethylformamide, chloroform and tetrahydrofuran;
the template agent comprises one or more of molecular sieve, magnesium oxide, nano calcium carbonate and fine pore silica gel.
S4: soaking the S2 powder in the S3 soaking solution, uniformly mixing and drying;
s5: carbonizing the S4 product at 800-1000 ℃, removing the template agent by acid or alkali treatment, and drying to obtain the core-shell carbon molecular sieve.
It is another object of the present application to provide a core-shell carbon molecular sieve comprising an outer shell carbon molecular sieve having a pore size of 0.6 to 3.5nm and an inner core layer carbon molecular sieve having a pore size of 0.4 to 0.5nm.
The application also provides application of the core-shell carbon molecular sieve in the aspect of gas chromatography methane separation columns.
Compared with the prior art, the invention has the following advantages:
1) The core-shell type carbon molecular sieve comprises an inner layer and an outer layer, when the content of heavy components in waste gas is high, the heavy components can be adsorbed by using the shell layer carbon molecular sieve with a large aperture, so that the influence on the core layer carbon molecular sieve is reduced, the influence on the next sample injection analysis of the chromatographic column is reduced, and meanwhile, the aging frequency and time of the chromatographic column are reduced.
2) After repeated long-time cyclic adsorption experiments of the chromatographic column, the residual amount of organic matters in the core-shell carbon molecular sieve is far lower than that of the conventional molecular sieve.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The technical solution of the present invention will be described in detail with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the core-shell carbon molecular sieve comprises the following steps:
s1: carbonizing coconut shells at 800 ℃, activating with alkali, and regulating and controlling the aperture by using benzene steam to prepare a nuclear layer carbon molecular sieve with the aperture of 0.4-0.5 nm;
s2: grinding the S1 nuclear layer carbon molecular sieve into powder with the particle size of 100 meshes for later use;
s3: preparing a phenolic resin, ethanol and an MCM molecular sieve into an impregnating solution according to the mass ratio of 1:2:0.5;
s4: soaking the S2 powder into the S3 soaking solution, uniformly mixing and drying;
s5: and (3) placing the S4 product into a rotary furnace at 800 ℃, carbonizing under the protection of inert gas, removing the MCM molecular sieve by using hydrofluoric acid treatment, and drying to obtain the core-shell carbon molecular sieve.
The prepared core-shell type carbon molecular sieve comprises an inner core layer carbon molecular sieve with the aperture of 0.4-0.5 nm and an outer shell layer carbon molecular sieve with the aperture of 0.6-3.5 nm, and the specific surface of the core-shell type carbon molecular sieve is 1500m 2 30% of the total particle diameter per gram, and 50% of the total particle diameter per gram, 0.4nm Kong Zhanbi and 1.0 to 2.5nm Kong Zhanbi.
Example 2
The preparation method of the core-shell carbon molecular sieve comprises the following steps:
s1: carbonizing polyamide acid at 800 ℃, activating with alkali, regulating the aperture by using methane steam, and preparing a nuclear layer carbon molecular sieve with the aperture of 0.4-0.5 nm;
s2: grinding the S1 nuclear layer carbon molecular sieve into powder with the particle size of 120 meshes for later use;
s3: preparing cellulose, dimethylformamide and nano calcium carbonate into an impregnating solution according to the mass ratio of 1:4:0.6;
s4: soaking the S2 powder into the S3 soaking solution, uniformly mixing and drying;
s5: and (3) placing the S4 product into a rotary furnace at 900 ℃, carbonizing under the protection of inert gas, removing nano calcium carbonate by using hydrofluoric acid treatment, and drying to obtain the core-shell carbon molecular sieve.
The prepared core-shell type carbon molecular sieve comprises an inner core layer carbon molecular sieve with the aperture of 0.4-0.5 nm and an outer shell layer carbon molecular sieve with the aperture of 0.6-3.5 nm, and the specific surface of the core-shell type carbon molecular sieve is 1480m 2 Per g, 35% at 0.4nm Kong Zhanbi and 48% at 1.0-2.5 nm Kong Zhanbi.
Example 3
The preparation method of the core-shell carbon molecular sieve comprises the following steps:
s1: carbonizing coal-based carbon at 800 ℃, activating with alkali, regulating the aperture by using ethane steam, and preparing a nuclear layer carbon molecular sieve with the aperture of 0.4-0.5 nm;
s2: grinding the S1 nuclear layer carbon molecular sieve into powder with the particle size of 150 meshes for later use;
s3: preparing a dipping solution from lignin, chloroform and fine pore silica gel according to the mass ratio of 1:8:0.8;
s4: soaking the S2 powder into the S3 soaking solution, uniformly mixing and drying;
s5: and (3) placing the S4 product into a rotary furnace at 1000 ℃, carbonizing under the protection of inert gas, removing fine pore silica gel by using hydrofluoric acid treatment, and drying to obtain the core-shell carbon molecular sieve.
The prepared core-shell type carbon molecular sieve comprises an inner core layer carbon molecular sieve with the aperture of 0.4-0.5 nm and an outer shell layer carbon molecular sieve with the aperture of 0.6-3.5 nm, and the specific surface of the core-shell type carbon molecular sieve is 1460m 2 31% of the material per gram, 31% of the material per 0.4nm Kong Zhanbi and 48% of the material per 1.0-2.5 nm Kong Zhanbi.
Example 4
The preparation method of the core-shell carbon molecular sieve comprises the following steps:
s1: carbonizing plant cellulose at 800 ℃, activating with alkali, regulating the aperture by using propane steam, and preparing a nuclear layer carbon molecular sieve with the aperture of 0.4-0.5 nm;
s2: grinding the S1 nuclear layer carbon molecular sieve into powder with the particle size of 150 meshes for later use;
s3: preparing a soaking solution from sucrose, tetrahydrofuran and magnesium oxide according to a mass ratio of 1:10:1;
s4: soaking the S2 powder into the S3 soaking solution, uniformly mixing and drying;
s5: and (3) placing the S4 product into a rotary furnace at 950 ℃, carbonizing under the protection of inert gas, removing magnesium oxide by using hydrofluoric acid treatment, and drying to obtain the core-shell carbon molecular sieve.
The prepared core-shell type carbon molecular sieve comprises an inner core layer carbon molecular sieve with the aperture of 0.4-0.5 nm and an outer shell layer carbon molecular sieve with the aperture of 0.6-3.5 nm, and the specific surface of the core-shell type carbon molecular sieve is 1500m 2 31% of the material per gram, 31% of the material per 0.4nm Kong Zhanbi, and 53% of the material per 1.0 to 2.5nm Kong Zhanbi.
Example 5
The preparation method of the core-shell carbon molecular sieve comprises the following steps:
s1: carbonizing a mixture of coconut shell carbon and polyacrylonitrile at 800 ℃, activating with alkali, and regulating the aperture by using toluene steam to prepare a nuclear layer carbon molecular sieve with the aperture of 0.4-0.5 nm;
s2: grinding the S1 nuclear layer carbon molecular sieve into powder with the particle size of 100 meshes for later use;
s3: preparing a phenolic resin and sucrose mixture, tetrahydrofuran and nano magnesium oxide into an impregnating solution according to the mass ratio of 1:6:0.6;
s4: soaking the S2 powder into the S3 soaking solution, uniformly mixing and drying;
s5: and (3) placing the S4 product into a rotary furnace at 850 ℃, carbonizing under the protection of inert gas, removing nano magnesium oxide by using hydrofluoric acid treatment, and drying to obtain the core-shell carbon molecular sieve.
The prepared core-shell type carbon molecular sieve comprises an inner core layer with the aperture of 0.4-0.5 nmCarbon molecular sieve and external shell layer carbon molecular sieve with pore diameter of 0.6-3.5 nm, and the specific surface of core-shell carbon molecular sieve is 1510m 2 Per g, 28% at 0.4nm Kong Zhanbi and 53% at 1.0-2.5 nm Kong Zhanbi.
Test example 1
The core-shell carbon molecular sieve prepared in example 1 was compared with the 5A molecular sieve commonly used in existing methane separation columns: the samples are respectively manufactured into a fixed bed form, the mixed waste gas of methane and tridecane is subjected to 5h cyclic adsorption experiments for 20 times at 180 ℃, and the residual amount of organic matters in the core-shell type carbon molecular sieve is 60% lower than that of the 5A molecular sieve through thermal weight comparison.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (8)
1. A method for preparing a core-shell carbon molecular sieve, which is characterized by comprising the following steps:
s1: carbonizing, activating and regulating aperture of the carbon precursor to prepare a nuclear layer carbon molecular sieve;
s2: grinding the nuclear layer carbon molecular sieve in the step S1 into powder for standby;
s3: preparing a shell raw material, an organic solvent and a template agent into an impregnating solution according to a proportion;
s4: soaking the powder in the step S2 into the soaking solution in the step S3, uniformly mixing and drying;
s5: carbonizing the S4 product, removing the template agent, and drying to obtain the core-shell carbon molecular sieve;
the carbon precursor comprises one or more of biomass, coal quality and high molecular polymer;
the aperture of the nuclear layer carbon molecular sieve is 0.4-0.5 nm;
the shell raw material comprises one or more of phenolic resin, cellulose, lignin and sucrose.
2. The method according to claim 1, wherein the pore diameter controlling substance comprises one or more of benzene, methane, ethane, propane and toluene.
3. The method according to claim 1, wherein the particle size of the powder in step S2 is 100 to 150 mesh.
4. The method of claim 1, wherein step S3 further satisfies one or more of the following conditions:
a. the organic solvent comprises one or more of ethanol, dimethylformamide, chloroform and tetrahydrofuran;
b. the template agent comprises one or more of molecular sieve, magnesium oxide, nano calcium carbonate and fine pore silica gel.
5. The preparation method of claim 1, wherein the mass ratio of the shell raw material, the organic solvent and the template agent in the step S3 is 1 (2-10) (0.5-1).
6. The method of claim 1, wherein step S5 satisfies one or more of the following conditions:
c. the carbonization temperature is 800-1000 ℃;
d. the template removing agent is treated by acid or alkali.
7. A core-shell carbon molecular sieve, characterized in that the carbon molecular sieve comprises an outer shell carbon molecular sieve and an inner core layer carbon molecular sieve; the pore diameter of the carbon molecular sieve of the outer shell layer is 0.6-3.5 nm, and the pore diameter of the carbon molecular sieve of the inner core layer is 0.4-0.5 nm.
8. Use of the core-shell carbon molecular sieve of claim 7 in a gas chromatographic methane separation column.
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| CN1030030A (en) * | 1987-06-22 | 1989-01-04 | 中国科学院山西煤炭化学研究所 | The method of making carbon molecular sieve used as chromatographic stationary phase from coal |
| CN101804979A (en) * | 2010-04-07 | 2010-08-18 | 煤炭科学研究总院 | Coal-based carbon molecular sieve and preparation method thereof |
| CN103691399A (en) * | 2013-12-18 | 2014-04-02 | 北京科技大学 | Preparation method of high-performance carbon molecular sieve for separating carbon dioxide/methane |
| CN107107030A (en) * | 2014-12-23 | 2017-08-29 | 埃克森美孚研究工程公司 | Sorbing material and application method |
| CN105084343A (en) * | 2015-08-14 | 2015-11-25 | 湖州新奥利吸附材料有限公司 | Preparation method for low-cost carbon molecular sieve |
| CN105776206A (en) * | 2016-05-04 | 2016-07-20 | 南京正森环保科技有限公司 | Lignin-based molecular sieve activated carbon and preparation method thereof |
| CN107055507A (en) * | 2017-04-28 | 2017-08-18 | 无锡德碳科技股份有限公司 | A kind of preparation method of carbon molecular sieve |
| CN108383100A (en) * | 2018-04-16 | 2018-08-10 | 郑州富龙新材料科技有限公司 | A kind of methane-rich carbon molecular sieve and preparation method thereof |
| CN110339811A (en) * | 2019-06-27 | 2019-10-18 | 浙江工业大学 | A kind of microorganism based carbon molecular sieve and the preparation method and application thereof |
| CN113041998A (en) * | 2021-03-18 | 2021-06-29 | 安徽理工大学 | Preparation method and application of anti-static carbon molecular sieve |
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