CN116116389A - Method for preparing ultra-microporous carbon material by utilizing chitosan, preparation method thereof and method for separating small molecular hydrocarbon with high selectivity - Google Patents
Method for preparing ultra-microporous carbon material by utilizing chitosan, preparation method thereof and method for separating small molecular hydrocarbon with high selectivity Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 59
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000000197 pyrolysis Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011343 solid material Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 230000003750 conditioning effect Effects 0.000 claims abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000005977 Ethylene Substances 0.000 claims description 23
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 239000001294 propane Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- -1 small-molecule hydrocarbon Chemical class 0.000 abstract description 13
- 150000001336 alkenes Chemical class 0.000 abstract description 12
- 229910052573 porcelain Inorganic materials 0.000 abstract description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 8
- 239000010935 stainless steel Substances 0.000 abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000012216 screening Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 20
- 239000011148 porous material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000007873 sieving Methods 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 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
- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical compound CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000013334 ultra-microporous metal-organic framework Substances 0.000 description 1
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Abstract
The invention discloses a preparation method of a super-microporous carbon material by utilizing chitosan, and a preparation method and a method for separating small-molecule hydrocarbon with high selectivity. The method mainly comprises the following steps: (1) preparation of hydrothermal carbon: mixing chitosan and deionized water, stirring, placing into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing into an oven for hydrothermal reaction, and carrying out suction filtration and drying to obtain hydrothermal carbon, thereby obtaining a solid material; (2) high temperature thermal conditioning pyrolysis: and (3) placing the solid material obtained in the step (1) into a porcelain boat, and performing high-temperature pyrolysis reaction at 600-900 ℃ in an inert atmosphere to obtain the ultra-microporous carbon material. The chitosan-based ultramicropore carbon material prepared by the invention completely maintains the skeleton morphology of chitosan, has high carbon yield, has the screening separation function of preferentially adsorbing olefin and almost completely rejecting alkane, has high adsorption selectivity and low adsorption heat, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of micromolecular alkene/alkane adsorption separation materials, in particular to an ultra-microporous carbon material for preparing high-selectivity separation ethylene/ethane and propylene/propane by using chitosan, and a preparation method and application thereof.
Background
Ethylene (C) 2 H 4 ) Is the most important raw material in petrochemical production, and is mainly used for producing rubber, films and other high-added-value organic chemicals. In 2016, the global production of ethylene exceeded 1.5 hundred million tons. Propylene (C) 3 H 6 ) Is a global second large chemical raw material next to ethylene, is not only a basic raw material of three large synthetic materials, but also a main raw material for producing bulk chemicals such as polypropylene, acrylonitrile, acrylic acid, propylene oxide and the like. Steam cracking is currently the most important process for producing ethylene and propylene, and even in future industrial production, steam cracking is still the process route with the greatest yield. Steam cracking is a process for preparing low-carbon olefins such as ethylene, propylene and the like by molecular chain cleavage and dehydrogenation of petroleum hydrocarbons at high temperature (750-900 ℃), high pressure and steam. During the cracking process, a certain amount of ethane (C) is produced with a small amount of other reactions 2 H 6 ) Propane (C) 3 H 8 ) And the like. To produce the polymer grade olefins (up to 99.5% purity), these alkane impurities must be separated. The separation of small molecular olefins/paraffins in industry is based on energy intensive cryogenic separation technology (ethylene/ethane: number of trays) with severe conditions>100. 23bar and 248K; propylene/propane: number of trays>200. 7-28bar and 183-258K). Ethylene/ethane separation and propylene/propane separation are considered to be one of seven separation technologies that change the world. Adsorption separation can be performed under milder conditions and has higher energy efficiency, and is a potential alternative method for separating small molecular olefins/alkanes. However, these small molecule hydrocarbon analogues have similar kinetic diameters
And physicochemical properties, and can be prepared with high olefin adsorption capacityAnd physical adsorbents with high olefin/alkane adsorption selectivity are extremely challenging.
Adsorbents including zeolite molecular sieves, metal organic framework Materials (MOFs) and porous carbon materials have been reported for adsorptive separation of small molecular olefins/alkanes. For ethylene/ethane separation, liu et al [ Yuzong Liu, yeng Wu, wanwen Liang et al Bimetallic ions regulate pore size and chemistry of zeolites for selective adsorption of ethylene from ethane [ J ]].Chemical Engineering Science,2020,220:115636]A series of Ca's are reported 2+ /Ag + Ion-exchanged zeolite with pore size in the range of 3.8 and
between them. The Ag-Ca-4A sample can realize C 2 H 4 /C 2 H 6 Near ideal molecular sieving with higher C 2 H 4 Adsorption capacity (3.7 mmol/g at 298K and 1 bar). However, the heat of adsorption of Ag-Ca-4A samples is as high as 65kJ/mol, and the energy consumption of the regeneration process is high. Lin et al [ Rui-Biao Lin, libo Li, hao-Long Zhou et al molecular sieving of ethylene from ethane using arigid metal-organic framework [ J ]].Nature Materials,2018,17:1128-1133]The preparation of the product is named [ Ca (C) 4 O 4 )(H 2 O)]MOF of (A) having rigid one-dimensional channels with a cross-sectional area of the channels +.>
Between->
And->
Between them, can effectively prevent C 2 H 6 Entering the pore canal, however, the higher synthesis cost limits the application of MOFs in the practical industry. Porous carbon has been widely used in the fields of adsorption and separation due to its low cost, good porosity and excellent stability. Currently, due to the large use of corrosive activators (KOH, znCl) in the synthesis process 2 Etc.), the pore size distribution of the carbon material is relatively broad, and thus is used for separation of C 2 H 4 /C 2 H 6 Generally exhibit poor separation selectivity. Gao et al [ Fei Gao, yaquan Wang, xiao Wang et al Ethylene/ethane separation by CuCl/AC adsorbent prepared using CuCl ] 2 as a precursor[J].Adsorption,2016,22:1013-1022]The introduction of unsaturated metal sites (Cu + ) After that, through metal site and C 2 H 4 Pi-complexation between c=c, enhancement and C 2 H 4 Thermodynamic affinity between them. C (C) 2 H 4 /C 2 H 6 The selectivity of (2) may be increased from 0.80 before modification to 69.42 after modification. However, the high heat of adsorption possessed by pi-complexation strong interactions results in recovery of C from the adsorbent 2 H 4 High energy consumption of the process. For propylene/propane separations, the existing materials are also subject to high heat of adsorption [ xiaoning methou, guangMiao, guangden Xu et al mixed (Ag + ,Ca 2 + )-LTA zeolite with suitable pore feature for effective separation of C 3 H 6 /C 3 H 8 [J].Chemical Engineering Journal,2022,450(1):137913]High synthesis cost [ Bin Liang, xin Zhang, yi Xie et al an Ultramicroporous Metal-Organic Framework for High Sieving Separation of Propylene from Propane [ J ]].J.Am.Chem.Soc,2020,142(41):17795–17801]Low selectivity [ Yafei Yuan, yongsheng Wang, xuelian Zhang et al Wiggling Mesopores Kinetically Amplify the Adsorptive Separation of Propylene/Propane [ J ]].Angew.Chem.Int.Ed,2021,60:19063–19067]Is not limited to the above-mentioned method.
Thus, the preparation of carbon materials with molecular sieve functions is a more efficient way to achieve high selectivity separation of small molecular olefins/paraffins and regeneration with low energy consumption.
Chitosan (CS) is cheap and readily available and originates from the deacetylation of chitin, the second most abundant natural polysaccharide on earth. Hydrothermal carbonization (HTC) processes mainly include dehydration, condensation, polymerization, and aromatization. The hydrothermal carbon synthesized by hydrothermal synthesis has higher purity, so that porous carbon with concentrated ultramicropore pore size distribution can be formed after pyrolysis.
For both ethylene/ethane and propylene/propane separation systems, most of the materials are currently based on the difference in affinity between the adsorbent and the guest molecule, i.e. thermodynamic separation. There are few reports of uniform pore size based carbon material adsorbents to achieve molecular sieving between guest molecules. In addition, research on high-selectivity separation and low-energy-consumption regeneration of small-molecule alkene/alkane is also rarely reported through synthesis parameter adjustment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing the ultra-microporous carbon material by utilizing chitosan for high-selectivity separation of small-molecular hydrocarbon, the ultra-microporous carbon material can realize high-selectivity adsorption separation of small-molecular olefin/alkane through a hydrothermal process and thermal regulation pyrolysis, the olefin adsorption heat of the material is low, the cyclic stability is good, the regeneration with low energy consumption is facilitated, the raw material price is relatively low, and the preparation process is simple and controllable.
The aim of the invention is achieved by the following technical scheme.
A method for preparing a microporous carbon material by utilizing chitosan for high-selectivity separation of small molecular hydrocarbons, comprising the following steps:
(1) Preparation of chitosan-based hydrothermal carbon: mixing chitosan and deionized water, stirring, loading into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100ml, and then placing into an oven for hydrothermal reaction to obtain hydrothermal carbon;
(2) High temperature thermal conditioning pyrolysis: and (3) placing the solid material obtained in the step (1) into a porcelain boat, and performing high-temperature pyrolysis reaction at 600-900 ℃ in an inert atmosphere to obtain the ultra-microporous carbon material.
Preferably, in the step (1), the mass ratio of the chitosan to the deionized water is 1:4-1:7.
Further preferably, the mass ratio of chitosan to deionized water is 1:4-1:5.
Preferably, in the step (1), the stirring time after the chitosan and the deionized water are mixed is 15-20min, and the stirring temperature is 20-30 ℃.
Preferably, in the step (1), the temperature of the hydrothermal reaction of the reaction kettle in the oven is 180-210 ℃ and the reaction time is 12-16h.
Preferably, in the step (1), deionized water used for suction filtration is 500ml, and the drying temperature is 90-110 ℃ and the time is 11-13h.
Preferably, in the step (2), the inert atmosphere is argon, nitrogen or a mixture gas of any mixing ratio of the argon and the nitrogen.
Preferably, in the step (2), the temperature of the carbonization reaction is 600 to 700 ℃.
Preferably, in the step (2), the temperature rising rate of the carbonization reaction is 5-10 ℃/min.
Preferably, in step (2), the carbonization reaction is carried out for a period of 1 to 4 hours, more preferably 1 to 2 hours.
Preferably, in the step (2), the chitosan-based ultra-microporous carbon material is obtained after carbonization reaction, so that the chitosan-based carbon material with excellent ethylene/ethane and propylene/propane adsorption separation performance can be directly prepared.
A supermicroporous carbon material produced by the above-described method.
The above-described ultra microporous carbon material is used for separating ethylene/ethane and propylene/propane gases.
The invention develops a new way, and provides a new method for designing and preparing a microporous carbon molecular sieve material for separating ethylene/ethane and propylene/propane gases with high selectivity. The chitosan is used as a raw material, and the pore size of the carbon material is accurately regulated and controlled through a series of processes such as hydrothermal carbonization, thermal regulation pyrolysis activation and system optimization, so that the sieving separation performance which is used for preferentially adsorbing olefin and almost completely rejecting alkane is prepared. Compared with MOFs material, the adsorption separation material has the advantages of stable structure and low cost, and has good industrial application prospect.
Compared with the prior art, the invention has the following advantages:
the chitosan-based carbon material prepared by the invention adopts a polymer with lower price, and the prepared ultra-microporous carbon material can meet the high-selectivity screening separation requirement of ethylene/ethane and propylene/propane through simple pre-synthesis process adjustment. Meanwhile, the carbon material prepared by the method has the advantages of narrow pore size distribution, low adsorption heat, good cycle stability and hydrothermal stability and excellent industrial application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the chitosan-based ultra-microporous carbon material prepared in example 1 and example 2.
FIG. 2 an ethylene-ethane adsorption isotherm plot (298K) of the chitosan-based ultra-microporous carbon material prepared in example 2.
FIG. 3 shows a propylene-propane adsorption isotherm plot (298K) of the chitosan-based microporous carbon material prepared in example 1.
FIG. 4 ethylene-ethane permeation diagram (298K) of the chitosan-based microporous carbon material prepared in example 2.
FIG. 5 an ethylene adsorption isotherm cycle chart (298K) of the chitosan-based ultra-microporous carbon material prepared in example 2.
FIG. 6 is an ethylene equivalent adsorption heat map of the chitosan-based ultra-microporous carbon material prepared in example 2.
Detailed Description
The invention is further described below with reference to the drawings and the detailed description, without restricting the invention thereto.
Example 1
6g of Chitosan (CS) and 40ml of deionized water were poured into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100ml, stirred at 25 ℃ for 15min for mixing, and then the reaction kettle was placed into an oven at 190 ℃ for reaction for 14h. After the reaction, the reaction vessel was taken out and cooled in air for 8 hours, and the materials in the vessel were poured out and suction-filtered, and washed with 500ml deionized water. The resulting hydrothermal product was dried in an oven at 100 ℃ for 12h. And (3) taking 0.6g of dried Hydrothermal Carbon (HCS) in a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, controlling the heating rate to be 5 ℃/min under the nitrogen atmosphere, heating to 600 ℃, and carrying out pyrolysis reaction for 1h to obtain the chitosan-based ultramicropore carbon material, and marking as a sample CNC-600.
Example 2
6g of Chitosan (CS) and 30ml of deionized water were poured into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100ml, stirred at 25 ℃ for 15min for mixing, and then the reaction kettle was placed into an oven at 190 ℃ for reaction for 14h. After the reaction, the reaction vessel was taken out and cooled in air for 8 hours, and the materials in the vessel were poured out and suction-filtered, and washed with 500ml deionized water. The resulting hydrothermal product was dried in an oven at 100 ℃ for 12h. And (3) taking 0.6g of dried Hydrothermal Carbon (HCS) in a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, controlling the heating rate to be 5 ℃/min under the nitrogen atmosphere, heating to 700 ℃, and carrying out pyrolysis reaction for 2 hours to obtain the chitosan-based ultramicropore carbon material, and recording as a sample CNC-700.
Example 3
6g of Chitosan (CS) and 40ml of deionized water were poured into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100ml, stirred at 25 ℃ for 15min for mixing, and then the reaction kettle was placed into an oven at 190 ℃ for reaction for 12h. After the reaction, the reaction vessel was taken out and cooled in air for 8 hours, and the materials in the vessel were poured out and suction-filtered, and washed with 500ml deionized water. The resulting hydrothermal product was dried in an oven at 100 ℃ for 12h. And (3) taking 0.6g of dried Hydrothermal Carbon (HCS) in a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, controlling the heating rate to be 5 ℃/min under the nitrogen atmosphere, and carrying out pyrolysis reaction for 2.5h after the temperature is raised to 800 ℃, so as to obtain the chitosan-based ultramicropore carbon material, which is marked as a sample CNC-800.
Example 4
6g of Chitosan (CS) and 40ml of deionized water were poured into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100ml, stirred at 25 ℃ for 15min for mixing, and then the reaction kettle was placed into an oven at 190 ℃ for reaction for 10h. After the reaction, the reaction vessel was taken out and cooled in air for 8 hours, and the materials in the vessel were poured out and suction-filtered, and washed with 500ml deionized water. The resulting hydrothermal product was dried in an oven at 100 ℃ for 12h. And (3) taking 0.6g of dried Hydrothermal Carbon (HCS) in a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, controlling the heating rate to be 5 ℃/min under the nitrogen atmosphere, heating to 900 ℃, and carrying out pyrolysis reaction for 2.5h to obtain the chitosan-based ultramicropore carbon material, and marking the chitosan-based ultramicropore carbon material as a sample CNC-900.
Example 5
6g of Chitosan (CS) and 30ml of deionized water were poured into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100ml, stirred at 25 ℃ for 15min for mixing, and then the reaction kettle was placed into an oven at 210 ℃ for reaction for 14h. After the reaction, the reaction vessel was taken out and cooled in air for 8 hours, and the materials in the vessel were poured out and suction-filtered, and washed with 500ml deionized water. The resulting hydrothermal product was dried in an oven at 100 ℃ for 12h. And (3) putting 0.6g of dried Hydrothermal Carbon (HCS) into a porcelain boat, putting into a high-temperature tube furnace, controlling the heating rate to be 5 ℃/min under the nitrogen atmosphere, heating to 700 ℃, and carrying out pyrolysis reaction for 2 hours to obtain the chitosan-based ultramicropore carbon material, which is marked as a sample CNC-700#.
Example 6
6g of Chitosan (CS) and 30ml of deionized water were poured into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100ml, stirred at 25 ℃ for 15min for mixing, and then the reaction kettle was placed into an oven at 230 ℃ for reaction for 14h. After the reaction, the reaction vessel was taken out and cooled in air for 8 hours, and the materials in the vessel were poured out and suction-filtered, and washed with 500ml deionized water. The resulting hydrothermal product was dried in an oven at 100 ℃ for 12h. And (3) putting 0.6g of dried Hydrothermal Carbon (HCS) into a porcelain boat, putting into a high-temperature tube furnace, controlling the heating rate to be 5 ℃/min under the nitrogen atmosphere, heating to 700 ℃, and carrying out pyrolysis reaction for 2 hours to obtain the chitosan-based ultramicropore carbon material, wherein the sample is marked as CNC-700.
Fig. 1 is a scanning electron microscope image of the materials in examples 1 and 2, and it can be seen from the image that chitosan, hydrothermal carbon and ultramicropore carbon materials CNC-600 and CNC-700 are all in a sheet shape, which shows that the preparation process is mild, and the carbon skeleton of the materials is not severely etched.
FIGS. 2 and 3 are ethylene ethane and propylene propane adsorption isotherms of the chitosan-based microporous carbon materials prepared in examples 2 and 1, and it is seen from the curves that the material sample CNC-700 has a sieving separation property of preferentially adsorbing ethylene while almost completely rejecting ethane. Likewise, material sample CNC-600 had sieving separation properties that preferentially adsorbed propylene while almost completely rejecting propane.
Fig. 4, 5 and 6 correspond to the permeation of the chitosan-based ultra-microporous carbon material CNC-700 prepared in example 2 to ethylene-ethane mixture (50%: 50%), adsorption isotherm cycle of ethylene and equivalent adsorption heat, respectively. From the images, the CNC-700 material can realize the effect of dynamically separating ethylene and ethane, has excellent ethylene adsorption cycle stability, has adsorption heat lower than 30kJ/mol and low regeneration energy consumption, and is suitable for being applied to the industrial actual adsorption separation process.
Claims (10)
1. A method for preparing a microporous carbon material by using chitosan, which is characterized by comprising the following steps:
(1) Preparation of hydrothermal carbon: mixing chitosan and deionized water, stirring, loading into a reaction kettle, then placing into a baking oven for hydrothermal reaction, and carrying out suction filtration and drying to obtain a solid material hydrothermal carbon;
(2) High temperature thermal conditioning pyrolysis: and (3) carrying out high-temperature pyrolysis reaction on the solid material obtained in the step (1) in an inert atmosphere to obtain the ultra-microporous carbon material.
2. The method for preparing a microporous carbon material from chitosan according to claim 1, wherein in the step (1), the mass ratio of chitosan to deionized water is 1:4-1:7.
3. The method for preparing a microporous carbon material using chitosan according to claim 1, wherein in the step (1), the stirring time after the chitosan is mixed with deionized water is 10-30min, and the stirring temperature is 20-40 ℃.
4. The method for preparing a microporous carbon material by using chitosan according to claim 1, wherein in the step (1), the temperature of the hydrothermal reaction of the reaction kettle in the oven is 170-230 ℃ and the reaction time is 10-20h.
5. The method for preparing a microporous carbon material by using chitosan according to claim 1, wherein in the step (1), the solvent used for suction filtration is deionized water, and the drying temperature is 80-120 ℃ and the time is 10-14h.
6. The method for preparing a microporous carbon material from chitosan according to claim 1, wherein in the step (2), the inert atmosphere is argon, nitrogen or a mixture of any mixing ratio of the argon and nitrogen.
7. The method for preparing a microporous carbon material using chitosan according to claim 1, wherein the temperature of the pyrolysis reaction in the step (2) is 600 to 900 ℃.
8. The method for preparing a microporous carbon material by using chitosan according to claim 1, wherein in the step (2), the heating rate of the pyrolysis reaction is 3-8 ℃/min, and the time of the pyrolysis reaction is 1-4h.
9. A supermicroporous carbon material produced by the method of any one of claims 1-8.
10. The application of the ultra-microporous carbon material of claim 9 to high selectivity separation of small molecular hydrocarbons including separation of ethylene/ethane and propylene/propane.
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| CN114288810A (en) * | 2021-11-30 | 2022-04-08 | 浙江大学 | Application of microporous carbon material in adsorption separation of olefin and alkane |
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| CN114288810A (en) * | 2021-11-30 | 2022-04-08 | 浙江大学 | Application of microporous carbon material in adsorption separation of olefin and alkane |
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