CN113148980A - Micron-grade carbon molecular sieve material with controllable pore diameter and prepared from polyhydroxy carbohydrate as raw material and preparation method thereof - Google Patents
Micron-grade carbon molecular sieve material with controllable pore diameter and prepared from polyhydroxy carbohydrate as raw material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 89
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- 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 75
- 239000011148 porous material Substances 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 46
- 150000001720 carbohydrates Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000004005 microsphere Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001338 self-assembly Methods 0.000 claims abstract description 19
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- -1 carbohydrate compound Chemical class 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 12
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- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
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- 239000013067 intermediate product Substances 0.000 claims description 11
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- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 5
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 5
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 5
- 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 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229930182830 galactose Natural products 0.000 claims description 5
- 239000008101 lactose Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 4
- 239000007833 carbon precursor Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000007740 vapor deposition Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 37
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 17
- 238000000926 separation method Methods 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 239000001294 propane Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical compound CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 3
- 239000003068 molecular probe Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000302413 Carum copticum Species 0.000 description 1
- 235000007034 Carum copticum Nutrition 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 150000004676 glycans Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
Abstract
The invention discloses an angstrom-level carbon molecular sieve material with controllable pore diameter and taking polyhydroxy carbohydrate as a raw material and a preparation method thereof. The method mainly comprises the following steps: (1) adding acid into distilled water to prepare aqueous solutions with different hydrogen ion concentrations, then adding a polyhydroxy carbohydrate compound, uniformly stirring and dispersing, placing the mixed solution in a closed environment of a reaction kettle, and carrying out medium-temperature hydrothermal self-assembly reaction to prepare uniform carbonaceous hydrated microspheres; (2) and (2) washing and drying the carbonaceous hydrated microspheres obtained in the step (1), performing constant-temperature controlled pyrolysis, and cooling to obtain the micron-grade carbon molecular sieve material with the controllable aperture. Compared with the limitation that the aperture is difficult to accurately regulate and control by the traditional carbon molecular sieve vapor deposition method, the carbon molecular sieve obtained by the preparation method disclosed by the invention is adjustable in the sub-angstrom level range of 4.2-7.0 angstrom, and the preparation method is simple in process and low in cost.
Description
Technical Field
The invention relates to the technical field of angstrom-level carbon molecular sieve chemistry, in particular to a preparation method of an angstrom-level carbon molecular sieve material which is low in cost, stable in structure, uniform in pore size distribution and capable of being regulated and controlled in a sub-angstrom level.
Background
As a class of carbonaceous porous materials mainly comprising micropores, Carbon Molecular Sieves (CMS) have wide application prospects in the aspects of air purification, gas separation, harmful gas removal and the like. The annual total demand of carbon molecular sieves in China exceeds 6000 tons, the industrial scale is continuously enlarged along with the continuous development of economy in China, and the demand level of the carbon molecular sieves is increased year by year. At present, the domestic carbon molecular sieve mainly takes coconut shells, coal and resin as raw materials, pores are formed by etching with an activating agent (carbon dioxide, water, potassium hydroxide and the like), and the pore diameter is adjusted by depositing pyrolytic carbon. The production process is complex, high in energy consumption, low in product quality and easy to cause environmental pollution.
Due to the characteristics of slit-shaped pore channels of the carbon molecular sieve, different adsorption kinetics are generated on different object molecules mainly through the size and shape difference of adsorbed molecules, so that the separation of different components is realized. Therefore, the pore size has a crucial influence on the adsorption capacity and separation selectivity of the carbon molecular sieve. At present, the porosity of the carbon molecular sieve is mainly adjusted by Chemical Vapor Deposition (CVD) in China. By pyrolyzing volatile unsaturated hydrocarbons (such as benzene, methyl benzene, methane, etc.), pyrolytic carbon is deposited at the orifice to reduce the pore size to improve the separation selectivity. For example, patent (CN103349973A) uses CO2Activating and pore-forming the carbon precursor by using CO mixed gas to obtain activated carbon with high specific surface area, and repeatedly introducing dimethylbenzene serving as a carbon deposition agent to modify a pore channel, so that the pore diameter is reduced, and the separation selectivity is improved; in the patent (CN104045083B), coconut shells are carbonized, crushed and formed, and then carbon tetrachloride is introduced into a rotary electric furnace to adjust the porosity, so that the coconut shell-based carbon molecular sieve is obtained.
Although CVD has been widely used for the preparation of carbon molecular sieves, it has disadvantages in that: the pore diameter is difficult to accurately control, and the slit hole is extremely easy to block by deposited carbon at the orifice, so that the pore volume is greatly reduced, and the adsorption capacity of gas is reduced. Meanwhile, the material still has wider pore size distribution in the micropore range, and contains a small amount of mesopores and macropores, so that the separation selectivity of gas is reduced.
Disclosure of Invention
In view of the above, the present invention provides a novel carbon molecular sieve production process. Based on the complex production process of the carbon molecular sieve of carbonization-activation-carbon deposition commonly used in the market, the invention creatively uses polyhydroxy carbohydrate with low cost as raw materials, forms homogeneous carbonaceous microspheres by hydrothermal self-assembly, adjusts the microsphere structure by adjusting the concentration of hydrogen ions in a reaction system, and finally matches with corresponding temperature for controlled pyrolysis. The carbon molecular sieve obtained by the method has uniform aperture, can be regulated and controlled in sub-angstrom level, and is suitable for screening and separating small molecular gases. Meanwhile, the production process is simple, the synthesis cost is low, and the method is beneficial to large-scale industrial production.
The purpose of the invention is realized by the following technical scheme.
A preparation method of an angstrom-scale carbon molecular sieve material with controllable pore diameter by taking polyhydroxy carbohydrate as a raw material comprises the following steps:
(1) hydrothermal self-assembly reaction: adding an acidic substance into distilled water to prepare an acidic aqueous solution with hydrogen ion concentration of 0-6 mol/L, then adding a polyhydroxy carbohydrate compound carbon precursor into the acidic aqueous solution, wherein the mass ratio of the polyhydroxy carbohydrate compound precursor to the distilled water is a preset mass ratio, fully and uniformly stirring, transferring the solution into a reaction kettle, and carrying out hydrothermal self-assembly reaction at the temperature of 180-200 ℃ to form uniform carbonaceous hydrated microspheres;
(2) high-temperature controlled thermal reduction: and (2) washing and drying the carbonaceous hydrated microspheres obtained in the step (1), removing intermediate products which are not reacted on the surface, protecting by inert gas, raising the temperature to 600-900 ℃ by program, performing controlled high-temperature annealing, and cooling to normal temperature to obtain the micron-grade carbon molecular sieve material with the pore diameter, wherein the pore diameter of the micron-grade carbon molecular sieve material can be adjusted by the hydrogen ion concentration.
Preferably, in step (1), the polyhydroxy sugar compound is fructose or the fructose and one or more of galactose, sucrose, maltose and lactose.
Preferably, in step (1), the polyhydroxy sugar compound is one or more of galactose, sucrose, maltose and lactose.
Preferably, in the step (1), the polyhydroxy sugar compound is a chitosan nitrogen-containing compound.
Preferably, in the step (1), the acidic substance is one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and more preferably, the acidic substance is hydrochloric acid with a mass fraction of 36.5%.
Preferably, in the step (1), the hydrogen ion concentration of the acidic aqueous solution is 0.1-6 mol/L.
Preferably, in the step (1), the hydrogen ion concentration of the acidic aqueous solution is 0.1-2 mol/L.
Preferably, in the step (1), the temperature of the hydrothermal self-assembly reaction is 180-200 ℃ and the time is 6-20 h.
Preferably, in the step (2), the inert gas is argon, nitrogen or helium.
Preferably, in the step (2), the controlled high-temperature annealing temperature is 600-. Preferably, in the step (2), the controlled high-temperature annealing temperature is 700-.
Preferably, in the step (2), the controlled high temperature annealing time is 0.5 to 4 hours, and more preferably 0.5 to 3 hours.
Preferably, the preset mass ratio is 1: 10.
The application also provides an angstrom-scale carbon molecular sieve material, which is prepared by the method in any one of the above.
Preferably, the pore diameter of the Hermite-grade carbon molecular sieve material is 4.2-7.0 Hermite. Wherein the pore diameter of the angstrom-scale carbon molecular sieve material can be adjusted by the concentration of hydrogen ions.
The micron-grade carbon molecular sieve material with the controllable ultramicropore aperture, which is prepared by the method, can be used in the field of adsorption and separation of small molecule gases.
The invention provides a novel establishment concept of the micron-grade carbon molecular sieve with controllable aperture, which is different from the traditional preparation method of the carbon molecular sieve. The method has the advantages that cheap and reproducible polyhydroxy carbohydrate is used as a carbon source, the structure of the hydrated carbon microsphere is adjusted by regulating the concentration of hydrogen ions in a hydrothermal self-assembly reaction system, and finally, a high-temperature thermal reduction process is carried out to obtain the novel controllable carbon molecular sieve material with uniform aperture.
Compared with the prior art, the invention has the following advantages:
(1) according to the synthesis process of the Hermite-grade carbon molecular sieve, the selected carbon source belongs to renewable resources, the price is low, the carbon source is easy to obtain, the synthesis process is simple to operate, the energy consumption is low, an activating agent is not required to be added, and the large-scale industrial production is facilitated.
(2) The selected saccharides are easier to prepare and have higher yield than other polysaccharides. Meanwhile, compared with other saccharides, the selected nitrogen-containing saccharide compound of chitosan has higher gas adsorption capacity and is more suitable for industrial application, and the amino group in the compound brings different effects to the final product.
(3) The carbon molecular sieve prepared by the invention has extremely high quality, the aperture is in the Hermite level range, the aperture is uniform, and the carbon molecular sieve can be in the sub-Hermite level
The adjustment and control within the range solve the difficulty that the aperture of the traditional carbon molecular sieve is difficult to be accurately adjusted.
(4) The carbon molecular sieve prepared by the invention is not easy to deposit carbon, has long service life, and the aperture is close to the dynamic diameter of small molecular hydrocarbon, so the carbon molecular sieve is very suitable for the field of screening and separating application of small molecular gas.
Drawings
FIG. 1 is a graph showing the pore size distribution of the carbon molecular sieve material prepared in example 2 of the present application.
Figure 2 is a pore size distribution diagram of a conventional carbon molecular sieve material.
FIG. 3 is an adsorption isotherm (298K) of ethylene ethane for the Ammi carbon molecular sieve material prepared in example 1 of the present application.
Fig. 4 is an adsorption isotherm (298K) of a conventional carbon molecular sieve material of the present application for ethylene ethane.
FIG. 5 is an adsorption isotherm (298K) of propylene propane by the Hermite grade carbon molecular sieve material prepared in example 2 of the present application.
FIG. 6 shows the adsorption isotherm (298K) of a conventional carbon molecular sieve material on propylene propane.
Fig. 7 is a schematic diagram of the reaction process provided herein.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
The method is characterized in that cheap and reproducible polyhydroxy carbohydrate is used as a carbon source, the structure of a hydrated carbon microsphere is adjusted by regulating the concentration of hydrogen ions in a hydrothermal self-assembly reaction system (as shown in figure 7), and finally, a high-temperature thermal reduction process is carried out to obtain the angstrom-level carbon molecular sieve material with uniform aperture and controllable diameter.
Example 1
(1) 0.833mL of concentrated hydrochloric acid (mass fraction: 36.5%) was added to 99.2mL of distilled water to prepare an aqueous solution having a hydrogen ion concentration of 0.1mol/L, and 10g of fructose was added thereto and sufficiently stirred for 30min to disperse the solution uniformly. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 16 hours at the constant temperature of 190 ℃, and then the obtained carbonaceous hydrated microspheres are washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (2) drying the carbonaceous hydrated microspheres in an oven at 100 ℃ overnight, then placing the dried carbonaceous hydrated microspheres in a high-temperature tube furnace, carrying out programmed heating to 800 ℃ for high-temperature pyrolysis for 2h at a heating rate of 5 ℃/min under the nitrogen atmosphere, and cooling to room temperature to obtain the No. 1 carbon molecular sieve material.
(3) The aperture of the obtained 1# carbon molecular sieve is mainly concentrated on
Wherein
The narrow aperture ratio of the range is more than 51 percent, the ethylene-ethane separation effect is good, the ethylene adsorption capacity reaches 1.80mmol/g and the ethane adsorption capacity is only 0.51mmol/g under normal temperature and normal pressure.
Example 2
(1) 0.0833mL of concentrated hydrochloric acid (mass fraction: 36.5%) was added to 99.9mL of distilled water to prepare an aqueous solution having a hydrogen ion concentration of 0.01mol/L, and 10g of fructose was added thereto and sufficiently stirred for 30min to disperse the solution uniformly. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 16 hours at the constant temperature of 190 ℃, and then the obtained carbonaceous hydrated microspheres are washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (2) drying the carbonaceous hydrated microspheres in an oven at 100 ℃ overnight, then placing the dried carbonaceous hydrated microspheres in a high-temperature tube furnace, carrying out programmed heating to 800 ℃ for high-temperature pyrolysis for 2h at a heating rate of 5 ℃/min under the nitrogen atmosphere, and cooling to room temperature to obtain the No. 2 carbon molecular sieve material.
(3) The pore diameter of the obtained 2# carbon molecular sieve is mainly concentrated on
Wherein
The narrow aperture ratio of the range is more than 59 percent, the device has the screening separation effect of only adsorbing propylene and not adsorbing propane, and the adsorption quantity of the device to the propylene reaches 2.22mmol/g at normal temperature and normal pressure.
Example 3
(1) 0.02633mL of concentrated hydrochloric acid (mass fraction: 36.5%) was added to 100mL of distilled water to prepare an aqueous solution having a hydrogen ion concentration of 0.0032mol/L, and 10g of fructose was added thereto and sufficiently stirred for 30min to disperse the mixture uniformly. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 16 hours at the constant temperature of 190 ℃, and then the obtained carbonaceous hydrated microspheres are washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (2) drying the carbonaceous hydrated microspheres in an oven at 100 ℃ overnight, then placing the dried carbonaceous hydrated microspheres in a high-temperature tube furnace, carrying out programmed heating to 800 ℃ for high-temperature pyrolysis for 2h at a heating rate of 5 ℃/min under the nitrogen atmosphere, and cooling to room temperature to obtain the No. 3 carbon molecular sieve material.
(3) The aperture of the obtained 3# carbon molecular sieve is mainly concentrated on
Wherein
The narrow pore diameter ratio of the range is more than 53%, and the adsorption capacity to propylene is 2.13mmol/g and the adsorption capacity to propane is less than 0.95mmol/g at normal temperature and normal pressure.
Example 4
(1) 0.0054mL of concentrated sulfuric acid (98% by mass) was added to 100mL of distilled water to prepare an aqueous solution having a hydrogen ion concentration of 0.001mol/L, and 10g of fructose was added thereto and sufficiently stirred for 30min to disperse the solution uniformly. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 16 hours at the constant temperature of 190 ℃, and then the obtained carbonaceous hydrated microspheres are washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (2) drying the carbonaceous hydrated microspheres in an oven at 100 ℃ overnight, then placing the dried carbonaceous hydrated microspheres in a high-temperature tube furnace, carrying out programmed heating to 800 ℃ for pyrolysis for 2 hours at a heating rate of 5 ℃/min under the nitrogen atmosphere, and cooling to room temperature to obtain the No. 4 carbon molecular sieve material.
(3) The aperture of the obtained 4# carbon molecular sieve is mainly concentrated on
Wherein
The narrow pore diameter ratio of the range is more than 50 percent, the molecular size of the catalyst is larger than that of propylene propane, the adsorption capacity to propylene at normal temperature and normal pressure reaches 2.53mmol/g, and the adsorption to propaneThe attached amount reaches 1.98 mmol/g.
Example 5
(1) 100mL of distilled water having a hydrogen ion concentration of about 0mol/L was added with 10g of fructose and the mixture was sufficiently stirred for 30min to disperse the fructose uniformly. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 16 hours at the constant temperature of 190 ℃, and then the obtained carbonaceous hydrated microspheres are washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (2) drying the carbonaceous hydrated microspheres in an oven at 100 ℃ overnight, then placing the dried carbonaceous hydrated microspheres in a high-temperature tube furnace, carrying out programmed heating to 800 ℃ for pyrolysis for 2 hours at a heating rate of 5 ℃/min under the nitrogen atmosphere, and cooling to room temperature to obtain the No. 5 carbon molecular sieve material.
(3) The aperture of the obtained 5# carbon molecular sieve is mainly concentrated on
Wherein
The narrow pore diameter ratio of the range is more than 51 percent, the narrow pore diameter ratio is larger than the molecular size of propylene propane, the adsorption capacity to propylene at normal temperature and normal pressure reaches 2.58mmol/g, and the adsorption capacity to propane is 2.02 mmol/g.
Example 6
(1) 8.33mL of concentrated hydrochloric acid (mass fraction: 36.5%) was added to 91.7mL of distilled water to prepare an aqueous solution having a hydrogen ion concentration of 1mol/L, and 10g of chitosan was added thereto and sufficiently stirred for 30min to disperse the mixture uniformly. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 20 hours at a constant temperature of 180 ℃, and then the obtained carbonaceous hydrated microspheres are washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (2) drying the carbonaceous hydrated microspheres in an oven at 100 ℃ overnight, then placing the dried carbonaceous hydrated microspheres in a high-temperature tube furnace, carrying out programmed heating to 700 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, carrying out high-temperature pyrolysis for 3h, and cooling to room temperature to obtain the No. 6 carbon molecular sieve material.
(3) The aperture of the obtained 6# carbon molecular sieve is mainly concentrated on
Wherein
The narrow pore diameter ratio of the range is more than 54 percent, the sieve separation effect of only adsorbing propylene and not adsorbing propane is realized, the adsorption capacity to the propylene is 2.58mmol/g and the adsorption capacity to the propane is less than 0.20mmol/g under normal temperature and pressure, and the adsorption capacity is higher than that of the nitrogen-free polyhydroxylated saccharide compound.
Example 7
(1) 0.054mL of concentrated sulfuric acid (mass fraction: 98%) is added into 99.9mL of distilled water to prepare an aqueous solution with hydrogen ion concentration of 0.01mol/L, 10g of galactose is added, and the mixture is fully stirred for 30min to be uniformly dispersed. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 16 hours at a constant temperature of 180 ℃, and then the obtained carbonaceous hydrated microspheres are washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (2) drying the carbonaceous hydrated microspheres in an oven at 100 ℃ overnight, then placing the dried carbonaceous hydrated microspheres in a high-temperature tube furnace, carrying out programmed heating to 900 ℃ for pyrolysis for 1h at a heating rate of 5 ℃/min under the nitrogen atmosphere, and cooling to room temperature to obtain the No. 7 carbon molecular sieve material.
(3) The aperture of the obtained 7# carbon molecular sieve is mainly concentrated on
Wherein
The narrow aperture ratio of the range is more than 50 percent, the device has the screening separation effect of only adsorbing propylene and not adsorbing propane, and the adsorption capacity to the propylene reaches 2.31mmol/g at normal temperature and normal pressure.
Example 8
(1) 0.0833mL of concentrated hydrochloric acid (mass fraction: 36.5%) was added to 99.9mL of distilled water to prepare an aqueous solution having a hydrogen ion concentration of 0.01mol/L, and 5g of fructose and 5g of sucrose were added thereto and sufficiently stirred for 30min to disperse them uniformly. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 16 hours at the constant temperature of 190 ℃, and then the obtained carbonaceous hydrated microspheres are washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (2) drying the carbonaceous hydrated microspheres in an oven at 100 ℃ overnight, then placing the dried carbonaceous hydrated microspheres in a high-temperature tube furnace, carrying out programmed heating to 800 ℃ for pyrolysis for 2 hours at a heating rate of 5 ℃/min under the nitrogen atmosphere, and cooling to room temperature to obtain the No. 8 carbon molecular sieve material.
(3) The aperture of the obtained 8# carbon molecular sieve is mainly concentrated on
Wherein
The narrow aperture ratio of the range is over 53 percent, the device has the screening separation effect of only adsorbing propylene and not adsorbing propane, and the adsorption capacity to the propylene reaches 2.16mmol/g at normal temperature and normal pressure.
Example 9
(1) 16.66mL of concentrated hydrochloric acid (mass fraction: 36.5%) was added to 83.34mL of distilled water to prepare an aqueous solution having a hydrogen ion concentration of 2mol/L, and 7g of maltose and 3g of lactose were added thereto and sufficiently stirred for 30min to disperse them uniformly. Then, the solution is subjected to hydrothermal self-assembly reaction in a closed environment of a reaction kettle, the reaction is carried out for 20 hours at a constant temperature of 180 ℃, and then the obtained hydrated carbon is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the hydrated carbon in an oven at 100 ℃ overnight, then placing the dried hydrated carbon in a high-temperature tube furnace, carrying out programmed heating to 700 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, carrying out high-temperature pyrolysis for 3h, and cooling to room temperature to obtain the No. 9 carbon molecular sieve material.
(3) The obtained No. 9 carbon molecular sieve material mainly focuses on the pore diameter
Wherein
The narrow pore diameter ratio of the range exceeds 50%, and propylene alone is adsorbed, and almost no propylene is adsorbedThe screening separation effect of the attached propane is that the adsorption capacity to the propylene is 1.89mmol/g and the adsorption capacity to the propane is less than 0.23mmol/g under normal temperature and normal pressure.
The method firstly adopts an ASAP2020 analyzer of American Micro company to characterize the pore structure of the material. The invention respectively uses carbon dioxide and nitrogen as molecular probes, and obtains the temperature less than or equal to 273K by testing the adsorption and desorption isotherm of carbon molecular sieve material to carbon dioxide
Pore size distribution of (2). Then utilizing the adsorption and desorption isotherm of the carbon molecular sieve material to nitrogen under 77K to obtain the micropores of the material
Mesopores
And large pores
So as to synthesize the overall aperture structure parameters of the material.
FIG. 1 is a plot of the pore size distribution of the carbon molecular sieve material of example 2, wherein (a) is the pore size obtained with carbon dioxide as the probe, and (b) is the pore size distribution of the micropore-mesopore-macropore obtained with nitrogen as the probe. The carbon molecular sieve prepared by the invention has the aperture mainly concentrated on the aperture analyzed from the figure 1
Wherein
The narrow pore diameter ratio of the range exceeds 59%, and the medium pore and the large pore are not contained, so that the high-quality glass has extremely high quality.
Fig. 2 is a diagram showing a pore size distribution of a carbon molecular sieve material obtained according to a conventional "carbonization-activation-carbon deposition" method, wherein (a) the diagram shows a pore size distribution of carbon dioxide as a molecular probe, and (b) the diagram shows a pore size distribution of micro-meso-macro pores as a molecular probe. From the analysis in the figure, the traditional carbon molecular sieve mainly has micropores, but still has wider pore size distribution in the micropore range, the pore size of the micropores is not easy to control in the specification, and the synthesis process is complex.
FIG. 3 is an adsorption isotherm of the carbon molecular sieve material of example 1 for ethylene ethane at 298K, with the pore size being primarily concentrated
In the narrow pore diameter range, the pore diameter of the micropores can be well controlled to be mainly between that of ethylene (kinetic diameter:
) And ethane (kinetic diameter:
) The molecular size is between the molecular size, so that the high-selectivity separation of ethylene and ethane bi-components can be realized, and the adsorption capacity of the ethylene reaches 1.80mmol/g under 1 bar.
FIG. 4 is an adsorption isotherm of a conventional carbon molecular sieve material for ethylene and ethane at 298K, which can simultaneously adsorb two components of ethylene and ethane due to its wide pore size distribution in the micropore range, and the adsorption capacity for ethylene reaches 2.31mmol/g at 1bar and the adsorption capacity for ethane reaches 1.97 mmol/g.
FIG. 5 is an adsorption isotherm of the carbon molecular sieve material of example 2 for propene propane at 298K, due to its predominantly concentrated pore size
In the narrow pore diameter range, the pore diameter of the micropores can be well controlled to be between the pore diameter of propylene (kinetic diameter:
) And propane (kinetic diameter:
) Between molecular sizes, and therefore can be performedThe propylene-propane bi-component is separated by sieving, and the adsorption capacity of the propylene reaches 2.22mmol/g under 1 bar.
FIG. 6 is an adsorption isotherm of a conventional carbon molecular sieve material for propylene propane at 298K, which can simultaneously adsorb two components of propylene propane due to its wide pore size distribution in the micropore range, and the adsorption capacity for propylene reaches 2.59mmol/g at 1bar and the adsorption capacity for propane reaches 1.82 mmol/g.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of an angstrom-scale carbon molecular sieve material with controllable pore diameter by taking polyhydroxy carbohydrate as a raw material is characterized by comprising the following steps:
(1) hydrothermal self-assembly reaction: adding an acidic substance into distilled water to prepare an acidic aqueous solution with hydrogen ion concentration of 0-6 mol/L, then adding a polyhydroxy carbohydrate carbon precursor into the acidic aqueous solution, fully and uniformly stirring, transferring the solution into a reaction kettle, and carrying out hydrothermal self-assembly reaction to form homogeneous carbonaceous hydrated microspheres;
(2) high-temperature controlled thermal reduction: and (2) washing and drying the carbonaceous hydrated microspheres obtained in the step (1), removing intermediate products which are not reacted on the surface, carrying out controlled high-temperature annealing by protecting with inert gas, carrying out temperature programming to the carbonization reaction temperature, and cooling to the normal temperature to obtain the Hermitian-grade carbon molecular sieve material, wherein the aperture of the Hermitian-grade carbon molecular sieve material is adjusted by the hydrogen ion concentration.
2. The method according to claim 1, wherein in step (1), the polyhydroxy sugar compound is fructose or fructose and one or more of galactose, sucrose, maltose and lactose.
3. The method according to claim 1, wherein in step (1), the polyhydroxylated saccharide compound is one or more of galactose, sucrose, maltose and lactose.
4. The method according to claim 1, wherein in step (1), the polyhydroxylated saccharide compound is a chitosan nitrogenous compound.
5. The method according to claim 1, wherein the acidic substance in step (1) is one or more of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
6. The method according to claim 1, wherein in the step (1), the hydrogen ion concentration of the acidic aqueous solution is 0.1 to 6 mol/L.
7. The method according to claim 1, wherein in the step (1), the temperature of the hydrothermal self-assembly reaction is 180-200 ℃ and the time is 6-20 h.
8. The method as claimed in claim 1, wherein in the step (2), the temperature raising rate of the temperature programming is 2-10 ℃/min, the carbonization reaction temperature is 600-900 ℃, and the reaction time is 0.5-6 h.
9. The method according to claim 1, wherein the mass ratio of the polyhydroxylated saccharide compound precursor to the distilled water is 1: 10.
10. The method of any one of claims 1 to 9, wherein the angstrom-scale carbon molecular sieve material has a pore size of 4.2-7.0 angstroms.
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| CN114249628A (en) * | 2021-12-31 | 2022-03-29 | 华南理工大学 | Separation method of CH3F and C3H8 |
| CN114275758A (en) * | 2021-11-30 | 2022-04-05 | 浙江大学 | Preparation method and application of microporous carbon material |
| CN114288810A (en) * | 2021-11-30 | 2022-04-08 | 浙江大学 | Application of microporous carbon material in adsorption separation of olefin and alkane |
| CN116116389A (en) * | 2023-01-13 | 2023-05-16 | 华南理工大学 | Method for preparing ultra-microporous carbon material by utilizing chitosan, preparation method thereof and method for separating small molecular hydrocarbon with high selectivity |
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| CN110395729A (en) * | 2019-08-27 | 2019-11-01 | 贵州大学 | A kind of preparation method for the ultra micro mesoporous activated carbon ball adsorbing coal bed gas methane |
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| CN114275758A (en) * | 2021-11-30 | 2022-04-05 | 浙江大学 | Preparation method and application of microporous carbon material |
| CN114288810A (en) * | 2021-11-30 | 2022-04-08 | 浙江大学 | Application of microporous carbon material in adsorption separation of olefin and alkane |
| CN114249628A (en) * | 2021-12-31 | 2022-03-29 | 华南理工大学 | Separation method of CH3F and C3H8 |
| CN116116389A (en) * | 2023-01-13 | 2023-05-16 | 华南理工大学 | Method for preparing ultra-microporous carbon material by utilizing chitosan, preparation method thereof and method for separating small molecular hydrocarbon with high selectivity |
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