CN113148980B - Pore-diameter-controllable Emi-level carbon molecular sieve material with polyhydroxy saccharide compound as raw material and preparation method thereof - Google Patents
Pore-diameter-controllable Emi-level carbon molecular sieve material with polyhydroxy saccharide compound as raw material and preparation method thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 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
- 239000000463 material Substances 0.000 title claims abstract description 44
- -1 saccharide compound Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002994 raw material Substances 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000004005 microsphere Substances 0.000 claims abstract description 36
- 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
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 238000001338 self-assembly Methods 0.000 claims abstract description 17
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 36
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 18
- 239000001294 propane Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
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- 238000000034 method Methods 0.000 abstract description 12
- 238000000197 pyrolysis Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract 1
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- 238000007740 vapor deposition Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 16
- 238000009826 distribution Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229930091371 Fructose Natural products 0.000 description 9
- 239000005715 Fructose Substances 0.000 description 9
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 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 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 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 description 3
- 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 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 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 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000000151 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
- 229930182830 galactose Natural products 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000008101 lactose Substances 0.000 description 3
- 239000003068 molecular probe Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 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 description 2
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 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 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011261 inert gas Substances 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
- 239000000523 sample Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 244000302413 Carum copticum Species 0.000 description 1
- 235000007034 Carum copticum Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an Emi-level carbon molecular sieve material with controllable pore diameter and taking polyhydroxy saccharide compound 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 polyhydroxy saccharide compounds, stirring and dispersing uniformly, placing the mixed solution into a closed environment of a reaction kettle, and performing medium-temperature hydrothermal self-assembly reaction to prepare uniform carbonaceous hydration microspheres; (2) And (3) washing and drying the carbonaceous hydrated microspheres obtained in the step (1), performing constant-temperature controlled pyrolysis, and cooling to obtain the controlled-aperture Emi-level carbon molecular sieve material. Compared with the limitation that the traditional carbon molecular sieve vapor deposition method is difficult to accurately regulate and control the aperture, the carbon molecular sieve obtained by the preparation method is adjustable in the sub-micron range of 4.2-7.0 meter, and has the advantages of simple process and low cost.
Description
Technical Field
The invention relates to the technical field of Emi-level carbon molecular sieve chemistry, in particular to a preparation method of an Emi-level carbon molecular sieve material which has low cost, stable structure and uniform pore size distribution and can be regulated and controlled at sub-Emi level.
Background
The Carbon Molecular Sieve (CMS) is used as a type of porous carbon material mainly comprising micropores, and has wide application prospects in the aspects of air purification, gas separation, harmful gas removal and the like. The total annual demand of the carbon molecular sieve in China exceeds 6000 tons, and along with the continuous development of the economy in China, the industrial scale is continuously enlarged, and the demand level of the carbon molecular sieve is also increased year by year. At present, domestic carbon molecular sieves mainly take coconut shells, coal and resin as raw materials, etch and make holes through activating agents (carbon dioxide, water, potassium hydroxide and the like), and then deposit pyrolytic carbon to adjust the aperture. The production process is complex, high in energy consumption, low in product quality and easy to cause environmental pollution.
Because of the characteristics of the slit-type pore canal of the carbon molecular sieve, the carbon molecular sieve mainly adsorbs moleculesDifferent adsorption kinetics are generated for different guest molecules, thereby achieving separation of different components. Thus, pore size has a critical impact on the adsorption capacity and separation selectivity of carbon molecular sieves. Currently, the porosity of carbon molecular sieves is primarily tuned domestically by Chemical Vapor Deposition (CVD). Pyrolytic carbon is deposited at the orifices by pyrolysis of volatile unsaturated hydrocarbons (e.g., benzene, toluene, methane, etc.) to reduce pore size to increase separation selectivity. For example, patent (CN 103349973A) uses CO 2 Activating and pore-forming the carbon precursor by the CO mixed gas to obtain active carbon with high specific surface area, and repeatedly introducing dimethylbenzene as a carbon deposition agent to modify pore channels, so that the pore diameter is reduced, and the separation selectivity is improved; the patent (CN 104045083B) carbonizes, pulverizes and forms the coconut shell, and then carbon tetrachloride is introduced into a rotary electric furnace to adjust the porosity, thus obtaining the coconut shell-based carbon molecular sieve.
Although CVD has been widely used for the preparation of carbon molecular sieves, it has disadvantages in that: the aperture is difficult to accurately control, and the slit holes are easily blocked by the deposited carbon at the aperture, 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 this, the present invention provides a novel process for producing carbon molecular sieves. Based on the complex carbon molecular sieve production process of carbonization-activation-carbon deposition commonly used in the market, the invention creatively takes polyhydroxy carbohydrate with low cost as a raw material, forms homogeneous carbonaceous microspheres by utilizing hydrothermal self-assembly, adjusts the microsphere structure by adjusting the concentration of hydrogen ions in a reaction system, and finally carries out controlled pyrolysis by matching with corresponding temperature. The carbon molecular sieve obtained by the method has uniform pore diameter, can be regulated and controlled at sub-Emi level, and is suitable for screening and separating small molecular gas. Meanwhile, the production process is simple, the synthesis cost is low, and the method is beneficial to large-scale industrial production.
The aim of the invention is achieved by the following technical scheme.
A preparation method of a controllable-pore-diameter Emi-level carbon molecular sieve material taking polyhydroxy saccharide compounds as raw materials comprises the following steps:
(1) Hydrothermal self-assembly reaction: adding an acidic substance into distilled water to prepare an acidic aqueous solution with the hydrogen ion concentration of 0-6 mol/L, and then adding a polyhydroxy saccharide compound carbon precursor into the acidic aqueous solution, wherein the mass ratio of the polyhydroxy saccharide compound precursor to the distilled water is a preset mass ratio, fully and uniformly stirring, transferring the solution into a reaction kettle, and performing hydrothermal self-assembly reaction at the temperature of 180-200 ℃ to form uniform carbonaceous hydrated microspheres;
(2) High temperature controlled thermal reduction: washing and drying the carbonaceous hydrated microsphere obtained in the step (1) to remove intermediate products with unreacted surfaces, then carrying out controlled high-temperature annealing by using inert gas protection and programming to 600-900 ℃, and cooling to normal temperature to obtain the Emi-level carbon molecular sieve material with the pore diameter, wherein the pore diameter of the Emi-level carbon molecular sieve material can be adjusted by the hydrogen ion concentration.
Preferably, in the step (1), the polyhydroxy saccharide compound is fructose or one or more of fructose, galactose, sucrose, maltose and lactose.
Preferably, in the step (1), the polyhydroxy saccharide compound is one or more of galactose, sucrose, maltose and lactose.
Preferably, in the step (1), the polyhydroxy saccharide 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 0.1-6mol/L.
Preferably, in the step (1), the hydrogen ion concentration of the acidic aqueous solution is 0.1-2mol/L.
Preferably, in the step (1), the temperature of the hydrothermal self-assembly reaction is 180-200 ℃ and the time is 6-20h.
Preferably, in step (2), the inert gas is argon, nitrogen or helium.
Preferably, in the step (2), the controlled high-temperature annealing temperature is 600-900 ℃, and the heating rate is 2-10 ℃/min. Preferably, in the step (2), the controlled high-temperature annealing temperature is 700-800 ℃, and the heating rate is 5 ℃/min.
Preferably, in step (2), the controlled high temperature annealing time is from 0.5 to 4 hours, more preferably from 0.5 to 3 hours.
Preferably, the preset mass ratio is 1:10.
The present application also provides an emma-sized carbon molecular sieve material made by the method of any of the above.
Preferably, the pore size of the Emi-grade carbon molecular sieve material is in the range of 4.2 Emi to 7.0 Emi. Wherein the pore size of the Emi-grade carbon molecular sieve material can be adjusted by the hydrogen ion concentration.
The Emi-level carbon molecular sieve material with controllable ultra-micropore aperture prepared by the method can be used in the field of adsorption separation of small molecular gas.
Unlike the traditional preparation method of carbon molecular sieve, the invention provides a novel construction concept for producing the Emi-level carbon molecular sieve with controllable aperture. The novel controllable carbon molecular sieve material with uniform aperture is obtained by regulating and controlling the concentration of hydrogen ions in a hydrothermal self-assembly reaction system by taking a renewable polyhydroxy saccharide compound with low price as a carbon source and finally performing high-temperature thermal reduction, the production process is energy-saving and environment-friendly, the obtained product has high quality and good performance, and the screening and separation of small molecular hydrocarbon can be realized.
Compared with the prior art, the invention has the following advantages:
(1) The synthesis process of the Emi-level carbon molecular sieve provided by the invention has the advantages that the selected carbon source belongs to renewable resources, the cost is low, the synthesis process is easy 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 yields than other polysaccharides. Meanwhile, compared with other saccharides, the selected chitosan nitrogen-containing saccharide compound has higher gas adsorption quantity, is more suitable for industrial application, and contains amino groups which bring different effects to the final product.
(3) The carbon molecular sieve prepared by the invention has extremely high quality, the pore diameter is in the range of the Ammi level, the pore diameter is uniform, and the carbon molecular sieve can be in the sub-Ammi levelThe difficulty that the aperture of the traditional carbon molecular sieve is difficult to accurately adjust is solved by regulating in the range.
(4) The carbon molecular sieve prepared by the invention is difficult to accumulate carbon, has long service life, and has a pore diameter close to the kinetic diameter of small molecular hydrocarbon, so that the carbon molecular sieve is very suitable for the application field of sieving and separating small molecular gas.
Drawings
FIG. 1 is a graph showing pore size distribution of an Emi-grade carbon molecular sieve material prepared in example 2 of the present application.
FIG. 2 is a graph of pore size distribution of a conventional carbon molecular sieve material.
FIG. 3 is an adsorption isotherm (298K) of ethylene ethane for the Emi-grade carbon molecular sieve material prepared in example 1 of the present application.
FIG. 4 is an adsorption isotherm (298K) of ethylene ethane for a conventional carbon molecular sieve material of the present application.
FIG. 5 is an adsorption isotherm (298K) of propylene propane for the Emi-grade carbon molecular sieve material prepared in example 2 of the present application.
FIG. 6 adsorption isotherm (298K) of conventional carbon molecular sieve material to propylene propane.
FIG. 7 is a schematic illustration of the reaction process provided herein.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
The low-cost and renewable polyhydroxy carbohydrate is used as a carbon source, the concentration of hydrogen ions in the hydrothermal self-assembly reaction system is regulated to adjust the structure of the hydrated carbon microsphere (shown in figure 7), and finally the uniform-aperture and controllable Emi-level carbon molecular sieve material is obtained through a high-temperature thermal reduction process, the production process is energy-saving and environment-friendly, the obtained product has high quality and good performance, and the screening separation of small-molecule hydrocarbon can be realized.
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 30 minutes to uniformly disperse the fructose. 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 microsphere is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the carbonaceous hydrated microspheres in a 100 ℃ oven overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, performing high-temperature pyrolysis for 2 hours, and cooling to room temperature to obtain the No. 1 carbon molecular sieve material.
(3) The pore size of the obtained No. 1 carbon molecular sieve is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 51%, the separation effect of ethylene and ethane is very good, the adsorption quantity of ethylene reaches 1.80mmol/g at normal temperature and normal pressure, and the adsorption quantity of ethane is only 0.51mmol/g.
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 stirred sufficiently for 30 minutes to disperse it 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 microsphere is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the carbonaceous hydrated microspheres in a 100 ℃ oven overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, performing high-temperature pyrolysis for 2 hours, and cooling to room temperature to obtain the No. 2 carbon molecular sieve material.
(3) The pore diameter of the obtained No. 2 carbon molecular sieve is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 59%, and the sieve separation effect of only absorbing propylene and not absorbing propane is achieved, and the absorption amount of 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 stirred sufficiently for 30 minutes to disperse it 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 microsphere is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the carbonaceous hydrated microspheres in a baking oven at 100 ℃ overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, performing high-temperature pyrolysis for 2 hours, and cooling to room temperature to obtain the No. 3 carbon molecular sieve material.
(3) The pore size of the obtained 3# carbon molecular sieve is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 53%, the adsorption quantity of propylene reaches 2.13mmol/g at normal temperature and normal pressure, and the adsorption quantity of propane is less than 0.95mmol/g.
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 stirred sufficiently for 30 minutes 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 microsphere is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the carbonaceous hydrated microspheres in a 100 ℃ oven overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, performing high-temperature pyrolysis for 2 hours, and cooling to room temperature to obtain the No. 4 carbon molecular sieve material.
(3) The pore diameter of the obtained No. 4 carbon molecular sieve is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 50%, the molecular size of the catalyst is larger than that of propylene propane, the adsorption capacity of propylene reaches 2.53mmol/g at normal temperature and normal pressure, and the adsorption capacity of propane reaches 1.98mmol/g.
Example 5
(1) 100mL of distilled water with a hydrogen ion concentration of about 0mol/L was used, and 10g of fructose was added thereto and stirred sufficiently for 30 minutes to disperse 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 microsphere is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the carbonaceous hydrated microspheres in a 100 ℃ oven overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, performing high-temperature pyrolysis for 2 hours, and cooling to room temperature to obtain the No. 5 carbon molecular sieve material.
(3) The pore size of the obtained No. 5 carbon molecular sieve is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 51%, and is larger than the molecular size of propylene propane, the adsorption quantity of propylene reaches 2.58mmol/g at normal temperature and normal pressure, and the adsorption quantity of propane is 2.02mmol/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 30 minutes to uniformly disperse the chitosan. 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 the constant temperature of 180 ℃, and then, the obtained carbonaceous hydrated microsphere is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the carbonaceous hydrated microspheres in a 100 ℃ oven overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 700 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, carrying out pyrolysis for 3 hours, and cooling to room temperature to obtain the No. 6 carbon molecular sieve material.
(3) The pore diameter of the obtained 6# carbon molecular sieve is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 54%, has the screening separation effect of only adsorbing propylene and not adsorbing propane, and has the adsorption quantity of propylene reaching 2.58mmol/g at normal temperature and normal pressure, the adsorption quantity of propane being less than 0.20mmol/g and being higher than the adsorption capacity of polyhydroxy saccharide compounds without nitrogen.
Example 7
(1) 0.054mL of concentrated sulfuric acid (98% by mass) 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 galactose was added thereto and stirred sufficiently for 30 minutes to disperse it 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 180 ℃, and then, the obtained carbonaceous hydrated microsphere is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the carbonaceous hydrated microspheres in a 100 ℃ oven overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 900 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, performing high-temperature pyrolysis for 1h, and cooling to room temperature to obtain the No. 7 carbon molecular sieve material.
(3) The pore size of the obtained 7# carbon molecular sieve is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 50%, has the screening separation effect of only absorbing propylene and not absorbing propane, and the absorption amount of 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 and sufficiently stirred for 30 minutes to uniformly disperse the aqueous solution. 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 microsphere is washed by 500mL of distilled water to remove unreacted intermediate products.
(2) And (3) drying the carbonaceous hydrated microspheres in a 100 ℃ oven overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, performing high-temperature pyrolysis for 2 hours, and cooling to room temperature to obtain the No. 8 carbon molecular sieve material.
(3) The pore size of the obtained 8# carbon molecular sieve is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 53%, and the sieve separation effect of only absorbing propylene and not absorbing propane is achieved, and the absorption amount of 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 and sufficiently stirred for 30 minutes to uniformly disperse the aqueous solution. 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 the 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 a 100 ℃ oven overnight, then placing the dried hydrated carbon in a high-temperature tube furnace, programming the temperature to 700 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, carrying out pyrolysis for 3 hours, and cooling to room temperature to obtain the 9# carbon molecular sieve material.
(3) The pore diameter of the obtained No. 9 carbon molecular sieve material is mainly concentrated inWherein->The narrow aperture ratio in the range exceeds 50%, and the sieve separation effect of only adsorbing propylene and hardly adsorbing propane is achieved, the adsorption quantity of propylene reaches 1.89mmol/g at normal temperature and normal pressure, and the adsorption quantity of propane is less than 0.23mmol/g.
The application firstly selects an ASAP2020 analyzer of Micro company in the United states to characterize the pore structure of the material. The invention respectively uses two gases of carbon dioxide and nitrogen as molecular probes, and obtains the adsorption and desorption isotherms of carbon dioxide at 273K by testing the carbon molecular sieve materialIs a pore size distribution of the particles. Then the adsorption and desorption isotherms of the carbon molecular sieve material to nitrogen at 77K are utilized to obtain micropores of the material>Middle hole->Big hole->To comprehensively obtain the overall pore diameter structural parameters of the material.
FIG. 1 is a graph showing pore size distribution of a carbon molecular sieve material in example 2, (a) shows pore size obtained by using carbon dioxide as a probe, and (b) shows pore size distribution of micropores-mesopores-macropores obtained by using nitrogen as a probe. From the analysis in FIG. 1, the carbon molecular sieve prepared by the invention has the pore diameter mainly concentratedWherein->The narrow aperture ratio of the range exceeds 59%, and the porous ceramic material does not contain mesopores and macropores, and has extremely high quality.
FIG. 2 is a graph showing pore size distribution of a carbon molecular sieve material obtained by a conventional "carbonization-activation-carbon deposition" method, (a) a graph showing pore size distribution of carbon dioxide as a molecular probe, and (b) a graph showing pore size distribution of micropores-mesopores-macropores of nitrogen as a molecular probe. From the analysis of the figure, the traditional carbon molecular sieve is mainly micropores, but still has wider pore size distribution in the micropore range, the pore size of micropores in the specification is not well controlled, and the synthesis process is complex.
FIG. 3 is an adsorption isotherm of ethylene ethane at 298K for the carbon molecular sieve material of example 1, since the pore size is primarily focusedCan better control the pore diameter of micropores within the narrow pore diameter range of ethylene (kinetic diameter:) And ethane (kinetic diameter: />) Between molecular sizes, thus can realizeThe ethylene bi-component is separated with high selectivity and the adsorption capacity of ethylene reaches 1.80mmol/g at 1 bar.
FIG. 4 shows adsorption isotherm of ethylene and ethane at 298K, which is a wide pore size distribution, so that the conventional carbon molecular sieve material can adsorb two components of ethylene and ethane simultaneously, the adsorption amount of ethylene reaches 2.31mmol/g at 1bar, and the adsorption amount of ethane reaches 1.97mmol/g.
FIG. 5 is an adsorption isotherm of propylene propane at 298K for the carbon molecular sieve material of example 2, due to its predominantly concentrated pore sizeThe pore diameter of the micropores can be well controlled within the narrow pore diameter range and is between propylene (kinetic diameter:. About.)>) And propane (kinetic diameter: />) The molecular size is between, so that the screening separation of propylene and propane bi-components can be realized, and the adsorption quantity of propylene reaches 2.22mmol/g at 1 bar.
FIG. 6 is an adsorption isotherm of a conventional carbon molecular sieve material for propylene propane at 298K, which can adsorb two components of propylene propane simultaneously because of 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 1.82mmol/g.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (1)
1. The preparation method of the pore-diameter-controllable Emi-level carbon molecular sieve material with the polyhydroxy saccharide compound as the raw material is characterized by comprising the following steps:
(1) Adding 8.33. 8.33mL concentrated hydrochloric acid with a mass fraction of 36.5% into 91.7. 91.7mL distilled water to prepare an aqueous solution with a hydrogen ion concentration of 1mol/L, adding 10g chitosan, and fully stirring for 30min to uniformly disperse the aqueous solution; then, carrying out hydrothermal self-assembly reaction on the solution in a closed environment of a reaction kettle, reacting at the constant temperature of 180 ℃ for 20h, and washing the obtained carbonaceous hydrated microspheres with 500mL distilled water to remove unreacted intermediate products;
(2) Drying the carbonaceous hydrated microspheres in a baking oven at 100 ℃ overnight, then placing the carbonaceous hydrated microspheres in a high-temperature tube furnace, programming the temperature to 700 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, pyrolyzing the carbonaceous hydrated microspheres at 3h, and cooling the carbonaceous hydrated microspheres to room temperature to obtain a carbon molecular sieve material;
(3) The narrow aperture ratio of the obtained carbon molecular sieve in the range of 4.2-5.0A exceeds 54%, the adsorption quantity of propylene reaches 2.58mmol/g at normal temperature and normal pressure, and the adsorption quantity of propane is less than 0.20 mmol/g.
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