CN117563378A - Application of multi-nitrogen azole porous material in one-step purification of ethylene in multi-component light hydrocarbon mixture - Google Patents
Application of multi-nitrogen azole porous material in one-step purification of ethylene in multi-component light hydrocarbon mixture Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000005977 Ethylene Substances 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 24
- 239000011148 porous material Substances 0.000 title claims abstract description 15
- 238000000746 purification Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 75
- 239000007789 gas Substances 0.000 claims abstract description 61
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 50
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 32
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 27
- 239000001294 propane Substances 0.000 claims abstract description 21
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000002474 experimental method Methods 0.000 claims description 15
- 230000035515 penetration Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 8
- PZKFSRWSQOQYNR-UHFFFAOYSA-N 5-methyl-1h-1,2,4-triazole Chemical compound CC1=NC=NN1 PZKFSRWSQOQYNR-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 238000003795 desorption Methods 0.000 abstract description 6
- 238000010926 purge Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- -1 propylene, ethylene, acetylene Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- AMXBISSOONGENB-UHFFFAOYSA-N acetylene;ethene Chemical group C=C.C#C AMXBISSOONGENB-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- 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
- B01D53/047—Pressure swing adsorption
-
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- 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
Abstract
The invention discloses an application of a multi-nitrogen azole porous material in purifying ethylene in a multi-component light hydrocarbon mixture in one step. The adsorption of propane, propylene, ethane and acetylene by the metal imidazole framework MAF-7 is higher than that of ethylene based on the customized geometric pore environment, so ethylene can be directly obtained from binary, ternary and five-membered gas mixtures. And further, the five-component mixed gas can be subjected to one-step purification of ethylene through a container filled with MAF-7 at a certain temperature and pressure, and desorption regeneration of the adsorbent is finished through inert gas purging or vacuumizing at room temperature. The material shows high ethane adsorption capacity and high ethane/ethylene adsorption ratio under the environmental condition, has excellent adsorption performance, can purify ethylene in a complex light hydrocarbon mixture in one step, and provides an effective method for designing an efficient and commercially valuable adsorbent to promote important industrial gas separation.
Description
Technical Field
The invention relates to the field of adsorption materials, in particular to a synthesis method of MAF-7 and application thereof in purifying ethylene in one step in a multicomponent light hydrocarbon mixture.
Background
Ethylene is an important industrial raw material in petrochemical industry, and byproducts such as propane, propylene, ethane, acetylene and the like are commonly produced in ethylene production. The ethylene purifying process includes liquid amine washing of carbon dioxide, catalytic hydrogenation of acetylene and low temperature rectification to eliminate ethane. However, the method is complicated in process and high in energy consumption, and the pressure swing adsorption technology is expected to obviously reduce the energy consumption in the separation process. Metal-organic frameworks (MOFs) with tailored porous structures and functions are considered ideal platforms for gas adsorption and separation.
In the prior art, more MOF materials have better gas adsorption performance, such as ZIF material metal-imidazole salt framework (MAF), also called zeolite-imidazole salt framework (ZIF), and the MOF material has the advantages of high stability, simple synthesis process, adjustable aperture, modifiable framework and the like, and is a zeolite-like topological structure formed by connecting transition metal (such as zinc and cobalt) ions with imidazole or derivatives thereof. However, the ZIF materials reported so far are difficult to combine with the problems of serious adsorption capacity and selectivity in the aspect of separating and purifying ethylene. Particularly, in multicomponent mixtures such as ternary mixtures (ethane/ethylene/acetylene and ethylene/acetylene/carbon dioxide) and quaternary mixtures (ethane/ethylene/acetylene/carbon dioxide), it is more difficult to directly separate high purity ethylene. As patent CN110237816B discloses a preparation method and application of a silver nitrate modified metal-organic framework adsorption material, although silver nitrate forms pi complex bond with c=c double bond in ethylene, the bond energy of pi complex bond is stronger than van der waals force, and at the same time, the adsorption capacity of the adsorption material for ethylene is higher than ethane, so as to realize separation of ethylene/ethane, but the adsorption selectivity is limited to binary components, and for multicomponent gas mixtures such as ethane/ethylene/acetylene ternary mixture, quaternary mixture to five-membered light hydrocarbon mixture, it is difficult to have high adsorption capacity and adsorption selectivity.
Therefore, it is necessary to develop a porous material having a one-step purification of ethylene from a multicomponent gas, particularly suitable for five-component light hydrocarbon mixtures (propane/propylene/ethane/ethylene/acetylene) and having low cost, high performance and high stability.
Technical content
The invention is realized by the following technical scheme:
the application of the multi-nitrogen porous material in one-step purification of ethylene in a multi-component light hydrocarbon mixture can effectively separate ethylene from a five-component light hydrocarbon mixture (propane/propylene/ethane/ethylene/acetylene);
the synthesis method of the polyazole porous material comprises the following steps: dripping aqueous solution of 3-methyl-1H-1, 2, 4-triazole into aqueous solution of zinc nitrate hexahydrate, dripping ammonia water into the mixed solution, stirring at room temperature, filtering, washing with methanol, and drying to obtain the compound with the chemical formula [ Zn (mtz) 2 ]Is a metal imidazole skeleton MAF-7 adsorbent;
further, the ratio of the amounts of the 3-methyl-1H-1, 2, 4-triazole and zinc nitrate hexahydrate is 2:1;
the addition amount of the ammonia water is 2-10% of the total volume of the mixed solution; in the mixed solution, the concentration of zinc is 0.01-0.1mol/L;
the invention prepares MAF-7 by adjusting the dosage of reaction raw materials and solvents, and performs amplified synthesis, in particular to a synthesis method of MAF-7 and application thereof in purifying ethylene in a multi-component light hydrocarbon mixture in one step.
Further, introducing a five-component mixed gas (propane/propylene/ethane/ethylene/acetylene) into an adsorption column filled with MAF-7 material, regulating the flow by a pressure valve and a flowmeter at the inlet of the adsorption column, and carrying out a dynamic adsorption penetration experiment under certain temperature and pressure; and monitoring the gas concentration at the outlet of the adsorption column in real time by adopting gas chromatography.
Further, the sample filled in the adsorption column is 0.5-1 g, the flow rate of the five-component mixed gas entering the adsorption column is 0-5 mL/min, and when the impurity gas is adsorbed on the adsorbent, the adsorption temperature is 0-25 ℃ and the pressure is 1bar or more.
As a further improvement of the efficient separation method, the MAF-7 can realize the efficient separation of ethylene in a five-component light hydrocarbon mixture (propane/propylene/ethane/ethylene/acetylene), can generate polymer grade ethylene product gas through one-step adsorption separation, and has the yield of high-purity ethylene of 10-20 cm obtained by one-time penetration experiment 3 /g。
Technical effects
According to the synthesis method of MAF-7, provided by the invention, the MAF-7 material is prepared by stirring at room temperature, simple stirring at room temperature, filtering and drying, and hundred-gram-grade products can be obtained at one time through the equal proportion expansion of metal and ligand, so that industrialized large-scale synthesis can be realized; compared with the reported metal imidazole porous material, the ethane selective adsorbent prepared by the invention has higher ethane adsorption capacity and ethane/ethylene separation selectivity. The adsorbent has the advantages of better structural stability, thermal stability, easy regeneration, high cycle stability and the like, so that the adsorbent is more suitable for industrialized separation operation. The MAF-7 prepared by the invention can realize one-step purification of ethylene in the five-component mixed gas, can generate polymer grade ethylene product gas through one-step adsorption separation, and has the yield of high-purity ethylene of 10-20 cm through one-time penetration experiment 3 And/g. Compared with other ethane selective materials, the MAF-7 prepared by the invention has low raw material price, the preparation process is green and simple, and the commercial application of purifying ethylene from complex light hydrocarbon mixtures in one step can be better realized.
Drawings
FIG. 1 is an SEM image of MAF-7 of example 1;
FIG. 2 is an XRD comparison of MAF-7 obtained in example 1 with simulated peaks;
FIG. 3 is a graph showing the adsorption and desorption of nitrogen at 77K for MAF-7 obtained in example 1;
FIG. 4 is an adsorption curve of MAF-7 obtained in example 1 to five-membered mixture gas at 298K;
FIG. 5 is an XRD pattern of MAF-7 obtained in example 1 after being subjected to different conditions;
FIG. 6 shows XRD patterns of MAF-7 obtained in example 1 after treatment at different pH values;
FIG. 7 is a graph showing the adsorption isotherms of multiple ethane cycles for MAF-7 obtained in example 1;
FIG. 8 is a diagram of an adsorption column and a penetration test apparatus;
FIG. 9 is a graph showing the breakthrough of the MAF-7 vs. ethane mixture obtained in example 1, ethylene=1:1 (v/v) at room temperature under pressure and dry conditions;
FIG. 10 is a graph showing the breakthrough curves of MAF-7 obtained in example 1 for ethane: ethylene: acetylene=9:90:1 (v/v/v) mixture at room temperature pressure and dry conditions, a being ethane: ethylene=1:1 (v/v);
FIG. 11 is a graph showing the penetration of MAF-7 obtained in example 1 into propylene/ethylene=1:1 (v/v) mixture at room temperature under pressure and dry conditions, a being ethane/ethylene=1:1 (v/v);
FIG. 12 is a graph showing the breakthrough of MAF-7 obtained in example 1 for a mixture of propane, propylene, ethylene, acetylene=9:10:10:70:1 (v/v/v/v/v) at room temperature pressure and under dry conditions.
Detailed Description
The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific embodiment is as follows: a synthetic method of MAF-7 comprises the following steps: dropwise adding an aqueous solution of 3-methyl-1H-1, 2, 4-triazole into an aqueous solution of zinc nitrate hexahydrate, dropwise adding ammonia water, stirring at room temperature, filtering, washing with methanol, and drying to obtain a compound with a chemical formula of [ Zn (mtz) 2 ]Metal imidazole framework (MAF) adsorbents.
A process for the one-step purification of ethylene from a five component light hydrocarbon mixture (propane/propylene/ethane/ethylene/acetylene) at room temperature comprising the steps of: introducing five-component mixed gas (propane/propylene/ethane/ethylene/acetylene) into an adsorption column filled with MAF-7 material, regulating the flow by a pressure valve and a flowmeter at the inlet of the adsorption column, and carrying out dynamic adsorption penetration experiment under certain temperature and pressure; and monitoring the gas concentration at the outlet of the adsorption column in real time by adopting gas chromatography. The desorption regeneration of the adsorbent is completed by inert gas purging at room temperature or under the condition of vacuumizing negative pressure.
In the synthesis process, the dosage of the metal salt, the ligand and the solvent is regulated to reduce the synthesis cost as much as possible, and in addition, the synthesis is simple, and the MAF-7 can be obtained by simply stirring at room temperature. The method for purifying ethylene from the five-component light hydrocarbon mixture (propane/propylene/ethane/ethylene/acetylene) in one step is simple in steps and wide in application range, can realize the high-efficiency separation of ethane and ethylene, can generate the polymerization grade ethylene gas through one-step adsorption separation, and is expected to realize the industrial application of MAF-7 materials.
In some specific embodiments, the molar weight of the 3-methyl-1H-1, 2, 4-triazole and the zinc nitrate hexahydrate is 2:1, the amount of added ammonia water is 2-10% of the total volume of the mixed solution, the reaction is carried out at room temperature for 3-5 hours, and the synthesis of 1g-100g can be realized.
MAF-7 material was prepared in some embodiments by simple stirring at room temperature, filtration, and drying. The invention is not limited to such yields in such proportions, and the same proportions of metal and ligand are expanded to yield hundred gram grade products at a time as are suitable for use in the invention.
In some embodiments the impurity gas is present in the mixed gas in a volume fraction of 0 to 50% and does not contain a zero value.
In some specific embodiments, the sample filled in the adsorption column is 0.5-1 g, the flow rate of the five-component mixed gas entering the adsorption column is 0-5 mL/min, and when the impurity gas is adsorbed on the adsorbent, the adsorption temperature is 0-25 ℃ and the pressure is 1bar or more.
In some specific embodiments, MAF-7 can realize the high-efficiency separation of ethylene in a five-component light hydrocarbon mixture (propane/propylene/ethane/ethylene/acetylene), and can generate polymer grade ethylene product gas through one-step adsorption separation, and the yield of high-purity ethylene obtained by one-time penetration experiment is 10-20 cm 3 /g。
Specific examples are exemplified below.
Example 1
10mL of an aqueous solution of 3-methyl-1H-1, 2, 4-triazole (0.168 g,2.0 mmol) was added dropwise to 10mL of an aqueous solution of zinc nitrate hexahydrate (0.294 g,1.0 mmol), followed by adding 1mL of aqueous ammonia (mass fraction 14%) with stirring. The above solution was stirred at room temperature for 4 hours, then filtered, washed with methanol and dried in air to give MAF-7 product.
Example 2
10mL of an aqueous solution of 3-methyl-1H-1, 2, 4-triazole (0.168 g,2.0 mmol) was added dropwise to 10mL of an aqueous solution of zinc nitrate hexahydrate (0.294 g,1.0 mmol), followed by 1.5mL of aqueous ammonia having a mass fraction of 14% with stirring. The above solution was stirred at room temperature for 4 hours, then filtered, washed with methanol and dried in air to give MAF-7 product.
MAF-7 prepared in example 1 was used as a test sample, and methanol was used for washing before testing the adsorption separation performance of the prepared sample. Washing the prepared white powder with methanol for 3 times, degassing and activating at 100deg.C under vacuum for 6 hr, and testing gas adsorption separation performance of the sample under pressure of 0-1bar.
To evaluate the actual separation effect of MAF-7 on five-membered mixture gas, dynamic breakthrough experiments were performed with the apparatus shown in FIG. 8 for ethane/ethylene, ethane/ethylene/acetylene, propylene/ethylene and propane/propylene/ethane/ethylene/acetylene mixtures, respectively. About 0.5 to 1g of the sample was charged into a stainless steel adsorption column having an inner diameter of 4mm and a length of 125 mm; purging residual gas in the pipeline by high-purity inert purge; the sample adsorption column is fixed in the indoor device, and the flow of the mixed gas is regulated by a pressure valve and a flowmeter at the inlet of the adsorption tower; monitoring the concentration of the gas at the outlet of the adsorption column in real time by adopting gas chromatography (490Micro GC,Agilent Technologies); the whole experiment is carried out at 0-25 ℃, and the ethane is ethylene (1:1, v/v); ethane: ethylene acetylene= (9:90:1, v/v/v); propylene: ethylene (1:1, v/v); the flow rate of the mixture of propane, propylene, ethane and ethylene and acetylene (9:10:10:70:1, v/v/v/v) is 0-5 mL/min.
To characterize the micro-morphology of MAF-7 material, SEM characterization of the product obtained in example 1 was performed, and the results are shown in FIG. 1.
To confirm the crystalline structure of the synthesized sample, XRD characterization was performed on the synthesized sample of example 1, and the results were compared with the simulated peaks of the MAF-7 theoretical crystalline structure, and the comparison results are shown in FIG. 2. As can be seen from the graph, the XRD diffraction peak of the MAF-7 prepared by the method is consistent with the simulated peak of the theoretical crystal form structure of the original structure, which proves that the MAF-7 material is successfully synthesized by the method.
To characterize the adsorption capacity of MAF-7 material for different gases, the product obtained in example 1 was tested for its adsorption performance for different gases using a Micromeritics ASAP 2020 instrument, the adsorption curve for each gas was measured for the product of example 1 at 298K, FIG. 3 shows the nitrogen adsorption and desorption curve for the material at 77K, and FIG. 4 shows the adsorption and desorption curves for the corresponding ethane, ethylene, propane, propylene and acetylene. As can be seen from FIGS. 3-4, MAF-7 has a relatively high BET specific surface area and exhibits adsorption separation performance for selectively adsorbing ethane, propane, propylene and acetylene over ethylene in the test temperature range, indicating that MAF-7 is an excellent ethylene purification adsorbent.
To test the stability of MAF-7 material, the acid-base stability and air stability of the material were tested, taking the product prepared in example 1 as an example. As can be seen from the XRD patterns shown in fig. 5 and 6, when the sample is exposed to different acid-base environments, respectively, or the sample is left in the air for half a year, the sample maintains the original crystal structure. FIG. 7 shows the cycle adsorption isotherm of ethane gas, and it can be seen that the performance of MAF-7 material is fully maintained through multiple adsorption and desorption cycle experiments.
(1) Adsorption separation effect experiment of two-component mixed gas ethane, ethylene and propylene
To test MAF-7 materials for ethane to ethylene (1:1, v/v) and propylene to ethylene (1:1, v/v); practical effects of gas mixture separation Using the product obtained in example 1 as an example, the above-described gas mixture separation experiment was performed on the product of example 1. The specific process is as follows: the mixed gas is precisely controlled to pass through an adsorption column (size phi 4 x 125 mm) filled with an adsorbent (sample size: 0.8 g) at a pressure (1.0 bar) and a flow rate (2 mL/min) through a pressure reducing valve and a gas mass flowmeter, the temperature of the adsorption column is controlled to be 298K, when the mixed gas starts to enter the adsorption column, timing is started at the same time, the tail gas concentration is monitored in real time at the tail end of the adsorption column through a chromatograph (GC-2014C, TCD detector), data are recorded until the mixed gas concentration reaches the initial concentration, and the two gases are considered to completely pass through, so that the adsorption is considered to be completed.
When the mixed gas is ethane/ethylene and propylene/ethylene (the volume fraction ratio is 1/1), the penetration curves of the adsorbent material are shown in figures 9 and 10, and it can be seen that the material can effectively remove ethane and propylene in the ethane-ethylene-propylene-ethylene mixed gas and effectively separate ethylene.
(2) Adsorption separation Effect experiment of three component gas (ethane: ethylene: acetylene) and five component gas (propane: propylene: ethane: ethylene: acetylene)
To test MAF-7 material vs. ethane: ethylene: acetylene= (9:90:1, v/v/v); the actual effect of the separation of the mixture of propane, propylene, ethane and ethylene and acetylene (9:10:10:70:1, v/v/v/v/v), the product of example 1 was used as an example, and the above-mentioned mixture separation experiment was performed on the product of example 1. The specific process is as follows: the mixed gas is precisely controlled to pass through an adsorption column (size phi 4 x 125 mm) filled with an adsorbent (sample size: 0.8 g) at a pressure (1.0 bar) and a flow rate (2 mL/min) through a pressure reducing valve and a gas mass flowmeter, the temperature of the adsorption column is controlled to be 298K, when the mixed gas starts to enter the adsorption column, timing is started at the same time, the tail gas concentration is monitored in real time at the tail end of the adsorption column through a chromatograph (GC-2014C, TCD detector), data are recorded until the mixed gas concentration reaches the initial concentration, and the two gases are considered to completely pass through, so that the adsorption is considered to be completed.
When the mixture is ethane: ethylene: acetylene= (9:90:1, v/v/v); the penetration curves of the adsorbent materials are shown in figures 11 and 12 respectively when propane, propylene, ethane and ethylene are acetylene (9:10:10:70:1, v/v/v/v/v), and as can be seen in figures 11 and 12, the materials can be used in the ternary and penta-ternary materials described aboveThe primary mixed gas realizes the one-step purification of ethylene, the polymer grade ethylene product gas can be generated through one-step adsorption separation, and the yield of the high-purity ethylene obtained through one-time penetration experiment is 10 cm to 20cm 3 /g。
As can be seen from the adsorption separation effects of the double components and the multiple components, the MAF-7 has good adsorption selectivity on ethylene, can have good separation effect on ethylene in the environment of double components and the multiple components, can achieve one-step adsorption separation, has excellent separation effect, and is indicated that the product of the invention can be suitable for industrial multiple component gas separation and can better realize the commercial application of purifying ethylene from complex light hydrocarbon mixtures in one step.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. The application of the multi-nitrogen porous material in one-step purification of ethylene in a multi-component light hydrocarbon mixture is characterized in that the multi-nitrogen porous material can efficiently separate ethylene from a five-component light hydrocarbon mixture (propane/propylene/ethane/ethylene/acetylene);
the synthesis method of the polyazole porous material comprises the following steps: dropwise adding an aqueous solution of 3-methyl-1H-1, 2, 4-triazole into an aqueous solution of zinc nitrate hexahydrate, dropwise adding ammonia water, stirring at room temperature, filtering, washing with methanol, and drying to obtain a compound with a chemical formula of [ Zn (mtz) 2 ]Is a metal imidazole skeleton MAF-7.
2. Use of a porous material of the polyazole type according to claim 1 for the one-step purification of ethylene in a multicomponent light hydrocarbon mixture, characterized in that the ratio of the amounts of 3-methyl-1H-1, 2, 4-triazole and zinc nitrate hexahydrate is 2:1; the addition amount of the ammonia water is 5% of the total volume of the mixed solution; in the mixed solution, the concentration of zinc is 0.01-0.1mol/L.
3. Use of a porous polyazole material according to claim 1 for the one-step purification of ethylene in a multicomponent light hydrocarbon mixture, comprising the steps of: introducing five-component mixed gas (propane/propylene/ethane/ethylene/acetylene) into an adsorption column filled with MAF-7 material, regulating the flow by a pressure valve and a flowmeter at the inlet of the adsorption column, and carrying out dynamic adsorption penetration experiment under certain temperature and pressure; and monitoring the gas concentration at the outlet of the adsorption column in real time by adopting gas chromatography.
4. The use of a porous material of the polyazole type according to claim 1 for purifying ethylene in a multicomponent light hydrocarbon mixture in one step, wherein the impurity gas in the mixed gas has a volume fraction of 0 to 50% and does not contain zero value.
5. The use of a porous material of the polyazole type for purifying ethylene in one step in a multicomponent light hydrocarbon mixture according to claim 1, wherein the sample filled in the adsorption column is 0.5-1 g, the flow rate of the five-component mixed gas entering the adsorption column is 0-5 mL/min, and the adsorption temperature is 0-25 ℃ and the pressure is 1bar or more when the impurity gas is adsorbed on the adsorbent.
6. The application of the multi-nitrogen porous material in one-step purification of ethylene in a multi-component light hydrocarbon mixture as claimed in claim 1, wherein MAF-7 can realize the efficient separation of ethylene in a five-component light hydrocarbon mixture (propane/propylene/ethane/ethylene/acetylene), and the polymerization grade ethylene product gas can be obtained through one-step column separation, and the yield of high-purity ethylene obtained through one-pass permeation experiments is 10-20 cm 3 /g。
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