CN118062825A - Granular carbon molecular sieve capable of sieving ethylene/ethane and preparation method and application thereof - Google Patents
Granular carbon molecular sieve capable of sieving ethylene/ethane and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000005977 Ethylene Substances 0.000 title claims abstract description 63
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 38
- 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 38
- 238000007873 sieving Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
- 238000003763 carbonization Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000197 pyrolysis Methods 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 150000001336 alkenes Chemical class 0.000 claims abstract description 19
- 238000012216 screening Methods 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000007833 carbon precursor Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 24
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims description 8
- 235000009566 rice Nutrition 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 7
- 244000060011 Cocos nucifera Species 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 5
- 241000533293 Sesbania emerus Species 0.000 claims description 4
- 244000062793 Sorghum vulgare Species 0.000 claims description 4
- 235000019713 millet Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 7
- 238000002791 soaking Methods 0.000 abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 241000209094 Oryza Species 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010420 shell particle Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 102100034275 Cx9C motif-containing protein 4 Human genes 0.000 description 1
- 101000711004 Homo sapiens Cx9C motif-containing protein 4 Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- B01D53/04—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 with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a granular carbon molecular sieve capable of sieving ethylene/ethane, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Crushing biomass carbon source particles, screening particles with target granularity, soaking the particles with a certain concentration of salt solution, filtering, drying, performing preliminary pyrolysis and carbonization on the granular carbon in an N 2 atmosphere at a certain temperature to prepare a carbon precursor with a certain structure and chemical composition, and cooling to room temperature; (2) Placing the granular carbon obtained after pyrolysis and carbonization in a C4 olefin mixed gas for adsorption; (3) Heating the porous carbon material to obtain the granular carbon molecular sieve capable of carrying out molecular sieve separation on ethylene/ethane.
Description
Technical Field
The invention belongs to the field of preparation of granular carbon molecular sieves, and particularly relates to a granular carbon molecular sieve capable of molecular sieving ethylene/ethane, and a preparation method and application thereof.
Background
Ethylene is the largest basic organic chemical worldwide, and the total yield of ethylene in 2022 is up to 2.18 hundred million tons/year worldwide, and China is the largest ethylene producing country worldwide. Ethylene and its derivatives to account for 70% of petrochemicals, the production and utilization level of ethylene is considered an important indicator of the state petrochemical development.
Ethylene is used as a chemical raw material for subsequent processing and production, and certain purity is required. Taking polyethylene production as an example, the raw material ethylene needs to reach a purity of more than 99.95%. Ethylene is generally produced industrially by pyrolysis of naphtha and steam, and the production of unreacted complete ethane impurities is unavoidable in the product, so that further separation and purification are required to produce polymerized pure ethylene. At present, a high-pressure low-temperature rectification process is mainly adopted for purifying ethylene. Because the main impurity is ethane, and the physical properties of the ethane and the ethylene are close, the high-pressure low-temperature rectification separation process has high energy consumption, and the separation cost occupies 70 percent of the total production cost. Therefore, development of an ethylene/ethane separation technology capable of efficiently and with low energy consumption at normal temperature is urgently required.
The adsorption separation technology can realize ethylene/ethane separation at normal temperature and normal pressure, and compared with the high-pressure low-temperature rectification technology, the separation energy consumption can be reduced by 75 percent. The adsorbent material is critical. However, the kinetic diameters of ethylene and ethane are respectivelyAndThe difference between the two is only/>The separation difficulty is significantly higher than that of propylene and propane (/ >)And). Thus a narrower pore structure and a more concentrated pore size distribution are required for the sieving separation of ethylene/ethane. At present, there are several metal-organic frameworks (MOFs), silver loaded zeolite molecular sieves and microporous carbon materials have been reported to have ethylene/ethane sieving properties. However, to be an industrial adsorbent, the adsorbent material must meet the requirements of good stability, excellent selectivity, high adsorption capacity, easy particle formation and low production cost at the same time. Most of the current MOFs materials are unstable and have high cost; zeolite molecular sieve is easy to accumulate carbon in olefin separation, and has poor circulation stability; du and the like take dopamine as raw materials, so that the complete screening separation (Du S,Huang J,Ryder M,et al.Probing sub-5Angstrom micropores in carbon for precise light olefin/paraffin separation[J].Nat Commun,2023,14(1):1197.). of the porous carbon material on ethylene/ethane is realized, however, the carbon molecular sieve mainly selects expensive dopamine as a carbon source, and the obtained sample is in a powder form and does not have the characteristic of direct industrial application. If molded by adding a binder, the adsorption capacity is lowered, and thus secondary pores are generated, resulting in a decrease in selectivity.
Disclosure of Invention
In order to prepare a granular carbon molecular sieve which is low in cost and can be directly applied to separating ethylene and ethane, the invention provides a universal preparation method of the granular carbon molecular sieve for separating ethylene/ethane. According to the invention, natural granular biomass is selected as a carbon source, and is subjected to crushing, screening and pretreatment, controlled pyrolysis carbonization is carried out, so that a microporous carbon material with specific pore size distribution is obtained, butadiene with the molecular size matched with ethane and mixed gas thereof are adsorbed into partial pore channels of the carbon material, and then carbon deposition reaction is carried out by heating, so that the pore channels which originally adsorb ethane are blocked, thus the pore structure is accurately regulated, selective ethylene adsorption without ethane adsorption is realized, and the granular carbon molecular sieve for efficiently sieving ethylene/ethane is prepared.
The aim of the invention is achieved by the following technical scheme.
A method for preparing a granular carbon molecular sieve capable of sieving ethylene/ethane, comprising the following steps:
(1) Crushing biomass carbon source particles, sieving, then impregnating with a salt solution, and then pyrolyzing and carbonizing the granular carbon precursor;
(2) And (3) placing the granular carbon treated in the step (1) in an atmosphere containing C4 olefin for adsorption, and then heating to enable the C4 olefin to carry out carbonization reaction on the surface of a pore canal of a carbon material, thus obtaining the granular carbon molecular sieve capable of sieving ethylene/ethane.
Preferably, the biomass carbon source particles of step (1) include, but are not limited to, one or more of coconut shell, coffee beans, palm shell, rice and millet; the granularity range of the biomass carbon source particles which are screened after being crushed is 10-40 meshes.
Preferably, the salt solution in the step (1) is mainly Fe salt, cu salt or a mixture of two salts, the concentration of the salt solution is 0.001-0.1mol/L, and the molar ratio of the two salts is Fe: cu=0.005-1:1, the time of impregnation is 1-8 hours, the temperature is room temperature to 40 ℃.
Preferably, the pyrolysis and carbonization in the step (1) are carried out under the atmosphere of N 2 and/or inert gas, the temperature of the preliminary pyrolysis and carbonization of the granular carbon is 250-900 ℃ and the time is 1-4 hours.
Preferably, the C4 olefins of step (2) include, but are not limited to, 1, 3-butadiene1-ButeneOne or two or more gases.
Preferably, in the atmosphere containing C4 olefins in the step (2), the volume ratio of 1, 3-butadiene is 1% -100%, and the balance is other C4 olefins and N 2.
Preferably, the total pressure in the atmosphere containing C4 olefins in step (2) is 0.1-2bar and the time of equilibrium adsorption is 0.5-6 hours.
Preferably, the heating temperature in the step (2) is 60-130 ℃, and the carbonization reaction time is 0.5-2 hours.
The granular carbon molecular sieve prepared by the preparation method of any one of the above, has molecular sieve separation performance on ethylene/ethane at normal temperature and pressure, and the adsorption amount ratio of ethylene/ethane is more than 8 (under 298K and 1 bar).
The granular carbon molecular sieve is applied to the adsorption separation of ethylene/ethane.
The invention has the following thought: selecting natural renewable granular biomass carbon sources such as coconut shells, palm shells, rice, millet and the like (which can reduce cost); the next challenge is that biomass granular carbon of different types, production places, growth years or parts has different initial structures and different paths of structural evolution after heating, which results in difficulty in controlling the pore channel size of carbon materials in batches on the secondary Emi precision by using the existing pyrolysis technology, and preparing qualified carbon molecular sieves. In order to overcome the problem, the biomass carbon source particles are crushed to a certain particle size, then a carbon precursor with a certain porosity and controllable pore size distribution is prepared by a pyrolysis carbonization method, then a certain amount of C4 olefin mixture is inserted into the pore channels of a material in an environment with a certain negative pressure, and is heated to a certain temperature under a closed condition, so that the olefin compounds form polymerization carbonization on the pore channel surfaces of the porous carbon material, and the pore channels with the size larger than the molecular dynamics diameter of ethane are sealed, thereby achieving the purposes of accurately regulating and controlling the size of the screening pore channels, leading the screening pore channels to repel ethane and only adsorb ethylene, and realizing the molecular screening separation of ethane and ethane.
The invention has the advantages that: the natural granular biomass is selected as a carbon source, so that the preparation cost is low; the micro-C4 olefin mixture is adopted and inserted into the pore canal of the material to control the size of the pore canal at one time, so that the method has the advantages of simple operation, accurate control, suitability for preparing carbon molecular sieves of biomass carbon sources of different sources, capability of avoiding the problem that the sieving pore canal of the carbon molecular sieves is difficult to control due to temperature sensitivity faced by a pyrolysis method, and easiness in industrial preparation; because natural granular biomass is selected as a carbon source, the prepared material is granular carbon material, subsequent molding is not needed, and the granularity can be controlled between 10 and 60 meshes (can be screened according to the need).
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The granular carbon molecular sieve prepared by the invention can realize molecular sieving of ethylene/ethane, has the adsorption capacity ratio of ethylene/ethane of more than 8 at normal temperature and normal pressure, and can meet the requirements of industrial separation and purification of ethylene.
(2) The granular carbon molecular sieve prepared by the invention has stable structure and low cost; the carbon molecular sieve prepared by the invention is granular, can be directly filled in an adsorption column separation device, and has the characteristic of direct engineering application.
(3) The invention adopts a unique principle to prepare the granular carbon molecular sieve capable of realizing molecular sieving of ethylene/ethane, and the unique sieving hole regulation strategy ensures that people can more widely select natural granular carbon sources to prepare the granular carbon molecular sieve with stable performance.
(4) The invention does not use adhesives and high pollution activators, and is environment-friendly.
Drawings
FIGS. 1-5 are adsorption isotherms of ethylene/ethane at 298K for the products obtained in examples 1-5.
FIG. 6 is an adsorption isotherm plot of ethylene/ethane at 298K for the products obtained in example 1 and comparative example 1.
FIG. 7 is an adsorption isotherm plot of ethylene/ethane at 298K for the product obtained in comparative example 2.
FIG. 8 is a graph showing the comparison of the ratios of the products obtained in examples 1 to 5 to the ethylene/ethane adsorption at 298K at1 bar.
FIG. 9 is a graph showing isothermal carbon dioxide adsorption/desorption at 273K of the products obtained in example 1 and comparative example 1.
FIG. 10 is a graph showing pore size distribution (GCMC model) of the product obtained in example 1 and comparative example 1 obtained by calculation of carbon dioxide adsorption/desorption isotherms at 273K.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The specific conditions are not noted in the examples of the present invention, and are carried out according to conventional conditions or conditions suggested by the manufacturer. The raw materials, reagents, etc. used, which are not noted to the manufacturer, are conventional products commercially available.
Example 1
Crushing a certain amount of rice, screening out 10-40 mesh particles, cleaning with clear water, filtering, soaking in an iron chloride/copper chloride mixed solution with the concentration of 0.001mol/L (wherein the molar ratio of the iron chloride to the copper chloride is=1:1) for 3 hours, filtering and drying, placing the dried rice in a tube furnace, heating the tube furnace to 300 ℃ in an N 2 atmosphere at a temperature of 5 ℃/min for pyrolysis and carbonization for 1 hour, and then heating to 800 ℃ at a temperature of 5 ℃/min for pyrolysis and carbonization for 1 hour, and cooling to obtain a microporous carbon material; placing the microporous carbon materials into a closed container, vacuumizing, filling 1bar of 1, 3-butadiene gas, statically adsorbing for 5 hours, heating the reactor to 100 ℃, maintaining for 1 hour, and cooling to room temperature to obtain a product marked CMC1#.
Example 2
Crushing a certain amount of initially carbonized coconut shell carbon, screening out 10-40 mesh particles, cleaning with clear water, filtering, soaking in an iron chloride/copper chloride mixed solution with the concentration of 0.1mol/L (wherein the molar ratio of the iron chloride to the copper chloride is=0.5:1) for 5 hours, filtering, drying, placing the dried coconut shell particles in a tubular furnace, heating the tubular furnace to 400 ℃ in an N 2 atmosphere at a temperature of 5 ℃/min for pyrolysis and carbonization for 1 hour, then heating to 700 ℃ at a temperature of 5 ℃/min for pyrolysis and carbonization for 3 hours, and cooling to obtain a microporous carbon material; placing the microporous carbon materials into a closed container, vacuumizing, filling 0.5bar of 1, 3-butadiene gas, statically adsorbing for 2 hours, heating the reactor to 120 ℃ for 1 hour, and then cooling to room temperature to obtain a product marked CMC2#.
Example 3
Crushing a certain amount of initially carbonized coffee beans, screening out 10-40 mesh particles, cleaning with clear water, draining, soaking in a ferric chloride/cupric chloride mixed solution with the concentration of 0.01mol/L (wherein the molar ratio of ferric chloride to cupric chloride is=0.1:1) for 8 hours, filtering, drying, placing the dried coffee bean particles in a tubular furnace, heating the tubular furnace to 850 ℃ in an N 2 atmosphere at the temperature of 3 ℃/min for pyrolysis carbonization for 1.8 hours, and cooling to obtain a microporous carbon material; the microporous carbon materials are placed in a closed container, 1.5bar of 1, 3-butadiene (2 percent) and 1-butene (2 percent) and N 2 (96 percent) mixed gas is filled after vacuumizing, and the mixture is kept stand for 6 hours and then heated at 60 ℃ for 0.5 hour, so that the product marked as CMC3#.
Example 4
Crushing a certain amount of primarily carbonized palm shell carbon, screening out 10-40 mesh particles, cleaning with clear water, filtering, soaking in an iron chloride/copper chloride mixed solution with the concentration of 0.003mol/L (wherein the molar ratio of the iron chloride to the copper chloride is=0.005:1) for 1 hour, filtering, drying, placing the dried coconut shell particles in a tubular furnace, heating the tubular furnace to 250 ℃ in an N 2 ℃ at a temperature rise rate of 5 ℃/min for pyrolysis carbonization for 1 hour, then heating to 700 ℃ at a temperature rise rate of 5 ℃/min for pyrolysis carbonization for 2 hours, and cooling to obtain a microporous carbon material; placing the microporous carbon materials into a closed container, vacuumizing, filling 0.1bar of 1, 3-butadiene gas, statically adsorbing for 1 hour, heating the reactor to 80 ℃ for 2 hours, and then cooling to room temperature to obtain a product marked CMC4#.
Example 5
Screening a certain amount of millet to obtain 10-40 mesh particles, cleaning with clear water, filtering, soaking in an iron chloride/copper chloride mixed solution with the concentration of 0.005mol/L (wherein the molar ratio of the iron chloride to the copper chloride is=0.5:1) for 4 hours, filtering and drying, placing the dried rice in a tube furnace, heating the tube furnace to 300 ℃ in an N 2 atmosphere at the temperature of 5 ℃/min for pyrolysis and carbonization for 1 hour, and then heating to 750 ℃ at the temperature of 5 ℃/min for pyrolysis and carbonization for 1 hour, and cooling to obtain a microporous carbon material; placing the microporous carbon materials into a closed container, vacuumizing, filling 2bar of 1, 3-butadiene gas, statically adsorbing for 4 hours, heating the reactor to 130 ℃ for 1 hour, and then cooling to room temperature to obtain a product marked CMC5#.
Comparative example 1
Crushing a certain amount of rice, screening out 10-40 meshes of particles, soaking in an iron chloride/copper chloride mixed solution with the concentration of 0.001mol/L (wherein the molar ratio of the iron chloride to the copper chloride is=1:1) for 3 hours, filtering and drying, placing the dried rice in a tube furnace, heating the tube furnace to 300 ℃ in an N 2 atmosphere at the temperature of 5 ℃/min for pyrolysis carbonization for 1 hour, heating to 800 ℃ at the temperature of 5 ℃/min for pyrolysis carbonization for 1 hour, and cooling to obtain the product obtained in the comparative example 1.
Comparative example 2
A certain amount of commercial coconut shell activated carbon is placed in a closed container, 1bar of 1, 3-butadiene gas is filled after vacuumizing, after static adsorption is carried out for 5 hours, the reactor is heated to 100 ℃ for 1 hour, and then cooled to room temperature, so that the product obtained in the comparative example 2 is obtained.
FIGS. 1-5 are adsorption isotherms of ethylene/ethane at 298K for the products obtained in examples 1-5. As can be seen, the granular carbon molecular sieve prepared by the invention hardly adsorbs ethane (less than 0.2 mmol/g), and shows excellent ethylene/ethane sieving separation effect. Wherein the product obtained in example 3 has higher ethylene adsorption capacity (1.38 mmol/g), the product obtained in example 5 has extremely low ethane adsorption capacity (0.014 mmol/g), and the product obtained in example 1 has both adsorption capacity and selectivity.
FIG. 6 is an adsorption isotherm plot of ethylene/ethane at 298K for the products obtained in example 1 and comparative example 1. As can be seen from the isothermal diagram, compared with the comparative example, the adsorption capacity of the product obtained in the example 1 to ethylene is reduced after the steps of standing, heating and the like in the C4 olefin atmosphere, but the adsorption capacity of ethane is reduced from 1.10mmol/g to 0.069mmol/g, so that the selectivity of the product to ethylene/ethane is greatly improved.
FIG. 7 is an adsorption isotherm plot of ethylene/ethane at 298 for the product obtained in comparative example 2. The product obtained in comparative example 2 has a certain ethylene/ethane separation performance, but no sieving effect is achieved.
FIG. 8 is a graph showing the comparison of the ratios of the products obtained in examples 1 to 5 to the ethylene/ethane adsorption at 298K at 1 bar. The products obtained in examples 1-5 all had an ethylene/ethane adsorption capacity ratio of greater than 8 at normal temperature and pressure, wherein the product obtained in example 5 had an ethylene/ethane adsorption capacity ratio of up to 60.29, exhibiting excellent ethylene/ethane sieving performance.
Fig. 9 and 10 are pore size distribution diagrams calculated by model GCMC of carbon dioxide adsorption and desorption isotherms at 273K of the products obtained in example 1 and comparative example 1. As can be seen from the carbon dioxide adsorption/desorption isotherm, the adsorption amount of carbon dioxide by the product obtained in example 1 was reduced compared to the comparative example after the steps of standing, heating, etc. in the C4 olefin atmosphere, because the pore volume of the material was reduced. As can be seen from the pore size distribution, the product obtained in example 1 is locatedAnd the pore structure of (c) fails, so that it exhibits excellent ethylene/ethane sieving performance.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A process for the preparation of a granular carbon molecular sieve capable of sieving ethylene/ethane comprising the steps of:
(1) Crushing biomass carbon source particles, sieving, then impregnating with a salt solution, and carrying out pyrolysis and carbonization on the particle carbon precursor;
(2) And (3) placing the granular carbon treated in the step (1) in an atmosphere containing C4 olefin for adsorption, and heating to enable the C4 olefin to carry out carbonization reaction on the surface of a pore canal of a carbon material, thus obtaining the granular carbon molecular sieve capable of screening ethylene/ethane.
2. The method of preparing a granular carbon molecular sieve from ethylene/ethane according to claim 1, wherein the biomass carbon source of step (1) comprises one or more of coconut shell, coffee beans, palm shell, rice and millet; the preferred particle size range of the biomass carbon source after particle breakage is 10-40 mesh.
3. The method for preparing the granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the salt solution in the step (1) is mainly Fe salt, cu salt or a mixture of two salts, the concentration of the salt solution is 0.001-0.1mol/L, and the molar ratio of the two salts is Fe: cu=0.005-1:1, the time of impregnation is 1-8 hours, the temperature is room temperature to 40 ℃.
4. The method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the pyrolysis and carbonization in the step (1) is performed under the atmosphere of N 2 and/or inert gas, the temperature of the granular carbon is 250-900 ℃ and the time is 1-4 hours.
5. The method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the C4 olefin in the step (2) comprises one or more of 1, 3-butadiene and 1-butene.
6. The method of preparing a granular carbon molecular sieve for ethylene/ethane screening according to claim 1, wherein in the atmosphere containing C4 olefins in step (2), the volume ratio of 1, 3-butadiene is 1% to 100%, and the balance is other C4 olefins and N 2.
7. The method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the total pressure in the atmosphere containing C4 olefins in step (2) is 0.1 to 2bar and the adsorption time is 0.5 to 6 hours.
8. The method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the heating temperature in the step (2) is 60-130 ℃, and the carbonization reaction time is 0.5-2 hours.
9. A granular carbon molecular sieve produced by the method of any one of claims 1-8.
10. A granular carbon molecular sieve as claimed in claim 9 for use in the adsorptive separation of ethylene/ethane.
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