WO2021169763A1 - Layered fluorine-containing metal-organic framework material for adsorbing and separating ethynyl and ethylene, and preparation method therefor and application thereof - Google Patents

Layered fluorine-containing metal-organic framework material for adsorbing and separating ethynyl and ethylene, and preparation method therefor and application thereof Download PDF

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WO2021169763A1
WO2021169763A1 PCT/CN2021/075162 CN2021075162W WO2021169763A1 WO 2021169763 A1 WO2021169763 A1 WO 2021169763A1 CN 2021075162 W CN2021075162 W CN 2021075162W WO 2021169763 A1 WO2021169763 A1 WO 2021169763A1
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acetylene
fluorine
metal
framework material
ethylene
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Chinese (zh)
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杨启炜
沈瑾
任其龙
柯天
杨亦文
张治国
鲍宗必
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浙江大学
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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
    • B01J20/223—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]
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
    • 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
    • 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

Definitions

  • the invention relates to the technical field of chemical separation, in particular to a layered fluorine-containing metal-organic framework material for the adsorption and separation of acetylene ethylene, and a preparation method and application thereof.
  • ethylene is widely used to synthesize plastics, rubber, polymer intermediates, etc.
  • the global output of ethylene was about 170 million tons, and its output is an important standard for measuring the development level of the country’s petrochemical industry.
  • Acetylene is often used for lighting, burning to produce high temperature to cut and weld metal; at the same time as the basic raw material to prepare acetaldehyde, acetic acid, synthetic fiber, synthetic rubber, etc.
  • Ethylene is mainly separated from petroleum cracked gas.
  • the common separation methods of ethylene acetylene mainly include selective hydrogenation, solvent absorption, cryogenic separation, and adsorption separation.
  • the selective hydrogenation method can be divided into pre-hydrogenation and post-hydrogenation according to the position of the hydrogenation step in the separation process.
  • the former such as the Chinese patent with application number CN201611247546.2
  • the overhead effluent from the pre-deethane pre-hydrogenation process enters the hydrogenation reactor for selective hydrogenation to remove alkynes and dienes
  • hydrogen such as the Chinese patent application number CN201511032200.6, the overhead effluent from the de-ethanizer enters an adiabatic reactor for selective hydrogenation to remove acetylene.
  • the solvent absorption method is representative of the Mehra process of American AET Company, which uses N-methylpyrrolidone (NMP), dimethylformamide (DMF), propylene carbonate, etc. as absorbents, but this method has serious organic solvent loss and efficiency.
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • propylene carbonate etc.
  • the problem of low energy consumption The cryogenic separation technology jointly developed by Air Products and Mobil is applied to the liquefaction catalytic cracking process. The ethylene yield can reach 90% to 98%, the process is complicated, and the cost is high.
  • Rui-Biao Lin et al. reported a [Zn(dps) 2 (SiF 6 )] material (UTSA-300a), where dps is 4,4'-dipyridine sulfide, which can selectively adsorb acetylene and can be used for Separation of acetylene/ethylene gas (Lin RB, Li L, Wu H, et al. Optimized Separation of Acetylene from Carbon Dioxide and Ethylene in a Microporous Material[J].Journal of the American Chemical Society,2017,139,8022-8028) .
  • the present invention provides a layered fluorine-containing metal-organic framework material for the adsorption and separation of acetylene and ethylene.
  • the material has permanent three-dimensional pores and has high selectivity and high capacity for acetylene. It is especially suitable for the adsorption and separation of trace acetylene, with good stability, simple preparation method and low preparation cost.
  • a layered fluorine-containing metal-organic framework material for the adsorption and separation of acetylene ethylene The general structural formula is ML 2 A, where M is a metal ion, L is a broken-line organic ligand, A is an inorganic fluorine-containing anion, and a metal ion M is bridged with the broken-line organic ligand L and inorganic fluorine-containing anion A to form a two-dimensional network with one-dimensional pores through coordination bonds, and adjacent two-dimensional networks are stacked by supramolecular interaction to form a layered three-dimensional network with permanent three-dimensional through-holes. structure;
  • the metal ion M is at least one of Cu 2+ , Fe 2+ , Co 2+ , Ni 2+ , and Zn 2+;
  • the polyline-type organic ligand L is at least one of 4,4'-dipyridine sulfoxide and 4,4'-dipyridine sulfone, and the structural formulas are respectively shown in the following formulas (I) and (II):
  • the sulfoxide or sulfone functional group contained in the polyline-type organic ligand L structure not only helps to obtain permanent three-dimensional pores, but also helps to enhance the interaction between the material and the gas molecule.
  • the inorganic fluorine-containing anion A is SiF 6 2- , GeF 6 2- , ZrF 6 2- , SnF 6 2- , TiF 6 2- , NbOF 5 2- , WO 2 F 4 2- , MoO 2 F 4 2 -At least one of.
  • the layered fluorine-containing metal-organic framework material has a permanent three-dimensional through-hole channel, and the average pore size of the material can be precisely adjusted by changing the types of inorganic fluorine-containing anions, organic ligands and metal ions.
  • the average pore diameter of the layered fluorine-containing metal-organic frame material is
  • the metal ion M is at least one of Cu 2+ and Ni 2+;
  • the polyline-type organic ligand L is 4,4'-dipyridylsulfone
  • the inorganic fluorine-containing anion A is at least one of SiF 6 2- , GeF 6 2- , TiF 6 2- , and NbOF 5 2-.
  • the layered fluorine-containing metal-organic framework material obtained by the above-mentioned preferred combination is more conducive to the adsorption and separation of ethylene acetylene, and the adsorption capacity and selectivity of low-concentration acetylene are higher.
  • the metal ion M is Cu 2+
  • the organic ligand is 4,4'-dipyridylsulfone
  • the inorganic fluorine-containing anion is SiF 6 2- ion.
  • the chemical formula of this special layered fluorine-containing metal-organic framework material is Cu(4,4'-dipyridylsulfone) 2 SiF 6 .
  • the metal ion M is Cu 2+
  • the organic ligand is 4,4'-dipyridylsulfone
  • the inorganic fluorine-containing anion is TiF 6 2- ion.
  • the chemical formula of this special layered fluorine-containing metal-organic framework material is Cu(4,4'-dipyridylsulfone) 2 TiF 6 .
  • the metal ion M is Cu 2+
  • the organic ligand is 4,4'-dipyridylsulfone
  • the inorganic fluorine-containing anion is NbOF 5 2- ion.
  • This special layered fluorine-containing metal-organic framework material can be called Cu(4,4'-dipyridylsulfone) 2 NbOF 5 .
  • the metal ion M is Ni 2+
  • the organic ligand is 4,4'-dipyridylsulfone
  • the inorganic fluorine-containing anion is TiF 6 2- ion.
  • This special layered fluorine-containing metal-organic framework material can be called Ni(4,4'-dipyridylsulfone) 2 TiF 6 .
  • the metal ion M is Ni 2+
  • the organic ligand is 4,4'-dipyridylsulfone
  • the inorganic fluorine-containing anion is NbOF 5 2- ion.
  • This special layered fluorine-containing metal-organic framework material can be called Ni(4,4'-dipyridylsulfone) 2 NbOF 5 .
  • the metal ion M is Zn 2+
  • the organic ligand is 4,4'-dipyridylsulfone
  • the inorganic fluorine-containing anion is NbOF 5 2- ion.
  • This special layered fluorine-containing metal-organic framework material can be called Zn(4,4'-dipyridylsulfone) 2 NbOF 5 .
  • the metal ion M is Cu 2+
  • the organic ligand is 4,4'-dipyridine sulfoxide
  • the inorganic fluorine-containing anion is MoO 2 F 4 2- ion.
  • This special layered fluorine-containing metal-organic framework material can be called Cu(4,4'-dipyridylsulfoxide) 2 MoO 2 F 4 .
  • the metal ion M is Cu 2+
  • the organic ligand is 4,4'-dipyridine sulfoxide
  • the inorganic fluorine-containing anion is NbOF 5 2- ion.
  • This special layered fluorine-containing metal-organic framework material can be called Cu(4,4'-dipyridylsulfoxide) 2 NbOF 5 .
  • the layered fluorine-containing metal-organic framework material of the present invention has good stability, simple preparation method, low preparation cost, excellent acetylene capture capacity and acetylene/ethylene selective separation performance, especially for the removal of trace amounts of acetylene at room temperature The effect is remarkable, and it has good industrial application prospects in the fields of gas adsorption, storage and separation.
  • the present invention also provides a method for preparing the layered fluorine-containing metal-organic framework material, which includes the steps:
  • the metal ion inorganic salt and inorganic fluorine-containing anion compound are dissolved in an organic solvent, deionized water or a mixture of deionized water and organic solvent according to the proportion to obtain a metal ion-inorganic fluorine-containing anion solution;
  • the organic ligand Dissolve in an organic solvent or a mixture of deionized water and an organic solvent according to the ratio to obtain an organic ligand solution;
  • the obtained metal-anion-organic framework material is filtered, washed, and dried to obtain the layered fluorine-containing metal-organic framework material.
  • the metal ion inorganic salt is at least one of metal ion M nitrate, chloride, acetate, carbonate, sulfate, perchlorate, and tetrafluoroborate.
  • the organic solvent is methanol, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, acetone, chloroform, dichloromethane, dimethylformamide At least one of sulfoxide, ethylene glycol, and glycerol.
  • the molar ratio of the metal ion inorganic salt, the inorganic fluorine-containing anion compound, and the organic ligand is 1:0.5-3:0.5-5.
  • the reaction temperature of the interface diffusion method and the solvothermal method are both 10-120°C, and the reaction time is both 1-72h. More preferably, the reaction temperature of the solvothermal method is 60-90°C and the reaction time is 12-24h.
  • the washing process is methanol washing and suction filtration, followed by soaking in methanol for 24 to 72 hours;
  • the drying process is: using vacuum desorption, purging with flowing gas (such as N 2 , He, Ar, etc.), the temperature is 25-120° C., and the time is 6-72 h.
  • flowing gas such as N 2 , He, Ar, etc.
  • the layered fluorine-containing metal-organic framework material particles prepared by the method of the invention have regular shapes and high water and thermal stability.
  • the present invention also provides the application of the layered fluorine-containing metal-organic framework material in the adsorption and separation of acetylene and ethylene.
  • the layered fluorine-containing metal-organic framework material is used as an adsorbent, and the gas containing acetylene and ethylene is used as an adsorbent. The mixture is contacted for adsorption separation.
  • the shape and size of the three-dimensional through pores of the layered fluorine-containing metal-organic framework material are similar to those of acetylene molecules, and the pores have high-density and negatively charged fluorine atoms, which can form strong specific hydrogen bonds with the acetylene molecules.
  • the adsorption capacity of this material for acetylene under low pressure is higher than that of all existing materials, and the selectivity is higher than that of most existing materials.
  • the application specifically includes the following steps: loading the desolventized layered fluorine-containing metal-organic framework material sample into the adsorption column; passing the gas mixture containing acetylene and ethylene into the adsorption column.
  • Ethylene has a weak interaction force with the adsorbent and flows out from the end of the adsorption column faster, while acetylene has a strong interaction force with the adsorbent, and slowly flows out from the end of the adsorption column after the adsorption reaches saturation. Due to the different interaction forces of the materials on the two gases, the effective separation of acetylene and ethylene in the gas mixture can be achieved.
  • the volume ratio of acetylene to ethylene in the gas mixture is 0.05:99.95 to 10:90.
  • the temperature of the adsorption separation is -5-60°C, and the pressure of the gas mixture is 0.5-5 bar. Further preferably, the temperature of the adsorption separation is 20-60°C, and the pressure of the gas mixture is 0.5-2 bar. Still further preferably, the temperature of the adsorption separation is 25-25°C, and the pressure of the gas mixture is normal pressure. Under the above-mentioned preferred conditions, various factors such as acetylene adsorption capacity, selectivity, adsorption rate, and energy consumption can be better considered.
  • the said gas mixture is not limited to containing acetylene and ethylene, but can also contain other gases such as water vapor, carbon dioxide, argon, nitrogen, oxygen, methane and helium.
  • acetylene is obtained by desorption.
  • the desorption conditions are: vacuum or inert gas (such as helium, nitrogen, etc.) atmosphere, and the desorption temperature is 25-120°C.
  • the heating temperature is too high, the structure of the adsorbent will be destroyed; if the temperature is too low, the adsorbate remaining in the adsorbent will not be completely removed.
  • the desorption temperature is 40-80°C.
  • the main advantages of the present invention include:
  • the layered fluorine-containing metal-organic framework material of the present invention has outstanding advantages such as good water and thermal stability, simple preparation method and low preparation cost, and has good industrial application prospects;
  • the layered fluorine-containing metal-organic framework material of the present invention has a strong force with acetylene molecules, a high adsorption capacity for acetylene under low acetylene partial pressure, and a high selectivity for acetylene/ethylene. Recyclable and other advantages;
  • This method can obtain high-purity ethylene products according to industrial needs, and the purity can reach more than 99.9999%;
  • the separation method provided by the present invention has outstanding advantages such as low energy consumption, mild conditions, and small equipment investment.
  • Example 1 is a schematic diagram of the crystal structure of the layered fluorine-containing metal-organic framework material obtained in Example 1;
  • 2A and 2B are respectively the adsorption isotherms of acetylene and ethylene and the adsorption heat maps of acetylene and ethylene under the layered fluorine-containing metal-organic framework material described in Example 1 at 298K;
  • Example 3 is a PXRD data diagram of the layered fluorine-containing metal-organic framework material described in Example 1;
  • C is the concentration of each component in the outlet gas
  • C 0 is the initial concentration of the raw gas
  • Example 5 is a schematic diagram of the crystal structure of the layered fluorine-containing metal-organic framework material obtained in Example 5;
  • 6A and 6B are respectively the adsorption isotherm of acetylene and ethylene and the adsorption heat map of acetylene and ethylene at 298K of the layered fluorine-containing metal-organic framework material described in Example 5;
  • Example 7 is a PXRD data diagram of the layered fluorine-containing metal-organic framework material described in Example 5;
  • Example 8 is the penetration curve diagram of the acetylene ethylene mixed gas of the layered fluorine-containing metal-organic framework material described in Example 6, in the ordinate, C is the concentration of each component in the outlet gas, and C 0 is the initial concentration of the raw material gas;
  • Example 9 is a schematic diagram of the crystal structure of the layered fluorine-containing metal-organic framework material obtained in Example 8.
  • Example 10 is the adsorption isotherm diagram of the layered fluorine-containing metal-organic framework material described in Example 8 for acetylene and ethylene at 298K;
  • Example 11 is a PXRD data diagram of the layered fluorine-containing metal-organic framework material described in Example 8.
  • Fig. 12 is a diagram showing the adsorption isotherm of the layered fluorine-containing metal-organic framework material described in Example 10 for acetylene at 298K;
  • Example 13 is a diagram showing the adsorption isotherm of the layered fluorine-containing metal-organic framework material described in Example 12 for acetylene at 298K;
  • Example 14 is a PXRD data chart of the layered fluorine-containing metal-organic framework material obtained in Example 15;
  • Example 15 is a PXRD data chart of the layered fluorine-containing metal-organic framework material obtained in Example 17.
  • the following single crystal X-ray diffractometer is used to obtain a single crystal X-ray structure: a Bruker Quest diffractometer equipped with a CMOS detector and a 1uS micro-focus Cu X-ray source.
  • the room temperature stirring method was used to synthesize 0.5mmol Cu(BF 4 ) 2 and 0.5mmol(NH 4 ) 2 TiF 6 in deionized water, and 1mmol 4,4'-dipyridylsulfone was dissolved in anhydrous methanol. After mixing and reacting at 25°C for 24 hours, crystals are obtained. The crystals obtained are filtered, washed with methanol, and dried to obtain Cu(4,4'-dipyridylsulfone) 2 TiF 6 .
  • Cu(4,4'-dipyridylsulfone) 2 TiF 6 is a metal-organic framework material with a layered three-dimensional structure.
  • the crystal structure is shown in Figure 1.
  • the metal copper ion and the organic ligand 4,4'-dipyridylsulfone form a pseudo-one-dimensional chain structure (ab plane), and the inorganic fluorine-containing anion TiF 6 2- is in the c-axis direction.
  • a two-dimensional network with one-dimensional pores is formed by bridging by coordination bonds, and adjacent two-dimensional networks are stacked by supramolecular action to form a layered three-dimensional structure with permanent three-dimensional through pores.
  • the material has interlayer pores and intralayer pores that are perpendicular to each other.
  • the intra-layer pores along the c-axis direction have an opening size of Figure 1C shows the interlayer channels along the a-axis, and the opening size is
  • the inorganic fluorine-containing anion TiF 6 2- provides negatively charged action sites for the three-dimensional through-holes within and between the layers, and strengthens the interaction with C 2 H 2 .
  • the adsorption isotherm of ethylene and acetylene for Cu(4,4'-dipyridylsulfone) 2 TiF 6 at 298K is shown in Figure 2A.
  • the adsorption capacity of Cu(4,4'-dipyridylsulfone) 2 TiF 6 for C 2 H 2 is larger than that of C 2 H 4 , especially in the low pressure area.
  • the adsorption capacity of C 2 H 2 measured at 0.01 bar and 1 bar was 2.96 mmol/g and 5.31 mmol/g.
  • the measured adsorption capacity of C 2 H 4 was only 0.37 mmol/g. g and 2.76mmol/g.
  • the adsorption heat Q st of C 2 H 2 is calculated to be 65.3 kJ/mol, which is much higher than 35.9 kJ/mol of C 2 H 4 , as shown in Figure 2B.
  • the Cu(4,4'-dipyridylsulfone) 2 TiF 6 material obtained in Example 1 was packed into a 5 cm long adsorption column (inner diameter of 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of acetylene: ethylene (volume ratio 1:99) mixed gas was passed into the adsorption column at 1.25mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the tube. Exhaust from the column outlet. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas.
  • the penetration curve is shown in Figure 4. After testing, ethylene penetrated in 48 minutes, and acetylene began to penetrate in 2200 minutes, and the dynamic adsorption capacity of acetylene was 1.9 mmol/g. The two gases are effectively separated. After 5 adsorption-regeneration cycles, the adsorption performance of this material is still stable.
  • the Cu(4,4'-dipyridylsulfone) 2 TiF 6 material obtained in Example 1 was packed into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the column. Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas. After regeneration, the adsorption column can be recycled.
  • the Cu(4,4'-dipyridylsulfone) 2 TiF 6 material obtained in Example 1 was packed into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of water: acetylene: ethylene (volume ratio 0.1:0.999:98.901) mixed gas was passed into the adsorption column at 1mL/min at 25°C, and gas chromatograph (GC 2010Pro, SHIMADZU) with flame ionization detector (FID) was used. ) Monitor the exhaust gas from the outlet of the pipe string. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
  • GC 2010Pro gas chromatograph
  • FID flame ionization detector
  • the methanol solution with 0.2mmol 4,4'-dipyridylsulfone was slowly dropped onto the DMF solution with 0.1mmol CuNbOF 5 , reacted at 25°C for 72h, filtered, washed with methanol, and dried to obtain Cu(4,4'-dipyridylsulfone) 2 NbOF 5 material.
  • Cu(4,4'-dipyridylsulfone) 2 NbOF 5 is a metal-organic framework material with a layered three-dimensional structure.
  • the metal copper ion and the broken-line organic ligand 4,4'-dipyridylsulfone form a pseudo-one-dimensional chain structure, and the inorganic fluorine-containing anion NbOF 5 2- is bridged by a coordination bond in the vertical direction to form a two-dimensional structure with one-dimensional pores.
  • Two-dimensional network, adjacent two-dimensional networks are stacked by supramolecular action to form a layered three-dimensional structure with three-dimensional through-holes.
  • the opening size of the pores in the material layer is The opening size of the interlayer channel is The inorganic fluorine-containing anion NbOF 5 2- provides negatively charged action sites for the three-dimensional through-holes in and between the layers, and strengthens the interaction with C 2 H 2 .
  • the adsorption isotherm of ethylene and acetylene for Cu(4,4'-dipyridylsulfone) 2 NbOF 5 at 298K is shown in Figure 6A.
  • the adsorption capacity of Cu(4,4'-dipyridylsulfone) 2 NbOF 5 for C 2 H 2 is larger than that of C 2 H 4 , especially in the low pressure area.
  • the adsorption capacity of C 2 H 2 was 2.23 mmol/g and 4.69 mmol/g measured at 0.01 bar and 1 bar, respectively.
  • the measured adsorption capacity of C 2 H 4 is only 0.18 mmol/g and 1.99 mmol/g.
  • the adsorption heat Q st of C 2 H 2 is calculated to be 57.6 kJ/mol, which is much higher than 36.9 kJ/mol of C 2 H 4 , as shown in Figure 6B.
  • the Cu(4,4'-dipyridylsulfone) 2 NbOF 5 material obtained in Example 5 was packed into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of acetylene: ethylene (volume ratio 1:99) mixed gas was passed into the adsorption column at 1.25 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the tube. Exhaust from the column outlet. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas.
  • the penetration curve is shown in Figure 8. After testing, ethylene penetrated in 35 minutes, acetylene began to penetrate in 1800 minutes, and the dynamic adsorption capacity of acetylene was 1.3 mmol/g. The two gases are effectively separated. After 5 adsorption-regeneration cycles, the adsorption performance of this material is still stable.
  • the Cu(4,4'-dipyridylsulfone) 2 NbOF 5 material obtained in Example 5 was packed into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC 2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the tube. Exhaust from the column outlet. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
  • GC 2010Pro gas chromatography
  • FID flame ionization detector
  • Cu(4,4'-dipyridylsulfone) 2 SiF 6 is a metal-organic framework material with a layered three-dimensional structure.
  • the metal copper ion and the organic ligand 4,4'-dipyridylsulfone and the inorganic fluorine-containing anion SiF 6 2- are bridged by coordination bonds to form a two-dimensional network with one-dimensional pores, and adjacent two-dimensional networks are stacked by supramolecular action A layered three-dimensional structure with three-dimensional through holes is formed.
  • the opening size of the pores in the material layer is The opening size of the interlayer channel is The inorganic fluorine-containing anion SiF 6 2- provides negatively charged action sites for the three-dimensional through-holes within and between the layers, and strengthens the interaction with C 2 H 2 .
  • the adsorption isotherm of ethylene and acetylene for Cu(4,4'-dipyridylsulfone) 2 SiF 6 at 298K is shown in Figure 10.
  • the adsorption capacity of Cu(4,4'-dipyridylsulfone) 2 SiF 6 for C 2 H 2 is larger than that of C 2 H 4 , especially in the low pressure area.
  • the adsorption capacity of C 2 H 2 was 2.65 mmol/g and 5.27 mmol/g measured at 0.01 bar and 1 bar, respectively. Under the same conditions, the measured adsorption capacity of C 2 H 4 is only 0.14 mmol/g and 1.99 mmol/g.
  • Figure 11 shows the PXRD pattern of Cu(4,4'-dipyridylsulfone) 2 SiF 6.
  • the Cu(4,4'-dipyridylsulfone) 2 SiF 6 obtained in Example 8 was loaded into a 5 cm long adsorption column (inner diameter of 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65° C. for 24 hours. Then, 1 bar of acetylene: ethylene (volume ratio 1:99) mixed gas was passed into the adsorption column at 1.25 mL/min at 25°C, and gas chromatography (GC 2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor Exhaust gas at the outlet of the pipe string. High-purity ethylene (greater than 99.9999%) gas can be obtained from the outflow gas. When the acetylene penetrates, the adsorption is stopped, and the adsorption column can be recycled after regeneration.
  • GC 2010Pro gas chromatography
  • FID flame ionization detector
  • Ni(4,4'-dipyridylsulfone) 2 TiF 6 at 298K for acetylene is shown in Figure 12.
  • the adsorption capacity of C 2 H 2 measured at 0.01 bar and 1 bar is 1.59 mmol/g and 3.85 mmol/g, respectively.
  • Ni(4,4'-dipyridylsulfone) 2 TiF 6 material obtained in Example 10 was loaded into a 5cm long adsorption column (inner diameter 4.6mm), and the sample was first purged with He flow (15mL/min) at 65°C for 24 hours . Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor from the column Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
  • NiNbOF 5 0.5mmol NiNbOF 5 was dissolved in DMF solution, 1mmol 4,4'-dipyridine sulfone was dissolved in anhydrous methanol, the two were mixed, reacted at 65°C for 24h to obtain crystals, and the crystals obtained were filtered and washed with methanol. And dry to obtain Ni(4,4'-dipyridylsulfone) 2 NbOF 5 .
  • Ni(4,4'-dipyridylsulfone) 2 NbOF 5 material obtained in Example 12 was loaded into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C for 24 hours . Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the column. Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
  • GC2010Pro gas chromatography
  • FID flame ionization detector
  • the methanol solution with 0.2mmol 4,4'-dipyridine sulfoxide was slowly dripped onto the ethylene glycol solution with 0.1mmol CuMoO 2 F 4 , reacted at 25°C for 72 hours, then filtered, methanol Washing and drying to obtain Cu(4,4'-dipyridylsulfoxide) 2 MoO 2 F 4 material.
  • Figure 14 shows the PXRD pattern of Cu(4,4'-dipyridylsulfoxide) 2 MoO 2 F 4.
  • Example 15 Put the Cu(4,4'-dipyridylsulfoxide) 2 MoO 2 F 4 material obtained in Example 15 into a 5 cm long adsorption column (inner diameter of 4.6 mm), and first purge the sample with He flow (15 mL/min) at 65°C 24 hours. Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the column. Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
  • GC2010Pro gas chromatography
  • FID flame ionization detector
  • the methanol solution with 0.2mmol 4,4'-dipyridine sulfoxide was slowly dropped onto the ethylene glycol solution with 0.1mmol CuNbOF 5 , reacted at 25°C for 72h, filtered, washed with methanol, Dry to obtain Cu(4,4'-dipyridylsulfoxide) 2 NbOF 5 material.
  • Figure 15 shows the PXRD pattern of Cu(4,4'-dipyridylsulfoxide) 2 NbOF 5.
  • the Cu(4,4'-dipyridylsulfoxide) 2 NbOF 5 material obtained in Example 17 was loaded into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C for 24 hours . Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the column. Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
  • GC2010Pro gas chromatography
  • FID flame ionization detector

Abstract

A layered fluorine-containing metal-organic framework material for adsorbing and separating acetylene and ethylene. The structural general formula is ML 2A, M being a metal ion, L being a broken line type organic ligand, A being an inorganic fluorine-containing anion, and the metal ion M being at least one of Cu 2+, Fe 2+, Co 2+, Ni 2+, and Zn 2+. The broken line type organic ligand L is at least one of 4,4'-dipyridylsulfoxide and 4,4'-dipyridylsulfone, and the inorganic fluorine-containing anion A is at least one of SiF 6 2-, GeF 6 2-, ZrF 6 2-, SnF 6 2-, TiF 6 2-, NbOF 5 2-, WO 2F 4 2-, and MoO 2F 4 2-. The layered fluorine-containing metal-organic framework material can be prepared by adopting an interface diffusion method, a solvothermal method or a room-temperature stirring method. The layered fluorine-containing metal-organic framework material is used as an adsorbent and is in contact adsorption with a gas mixture containing acetylene and ethylene, and efficient separation of acetylene/ethylene can be realized at room temperature, low acetylene content and low acetylene partial pressure.

Description

一种用于吸附分离乙炔乙烯的层状含氟金属-有机框架材料及其制备方法和应用Layered fluorine-containing metal-organic frame material for adsorption and separation of acetylene ethylene, and preparation method and application thereof 技术领域Technical field
本发明涉及化工分离技术领域，具体涉及一种用于吸附分离乙炔乙烯的层状含氟金属-有机框架材料及其制备方法和应用。The invention relates to the technical field of chemical separation, in particular to a layered fluorine-containing metal-organic framework material for the adsorption and separation of acetylene ethylene, and a preparation method and application thereof.
背景技术Background technique
乙烯作为世界上产量最大的化学品之一，广泛用于合成塑料、橡胶、聚合物中间体等，2018年，全球乙烯产量约在1.7亿吨，其产量是衡量国家石油化工发展水平的重要标准之一，被称为“石油化工之母”。乙炔常用于照明，燃烧产生高温以切断及焊接金属；同时作为基本原料制备乙醛、醋酸、合成纤维、合成橡胶等。乙烯主要从石油裂解气中分离获得，在进一步分离得到聚合级乙烯(乙炔含量小于40ppm)的过程中，少量的乙炔存在，就会使乙烯聚合过程中使用的催化剂中毒，缩短催化剂的使用寿命，与此同时生成副产物降低所生成的聚乙烯的品质。另外，乙炔会与金属反应生成金属乙炔化物，阻碍气体流动甚至引起爆炸，因此需要从乙烯乙炔混合气中脱除痕量乙炔。As one of the world’s largest chemicals, ethylene is widely used to synthesize plastics, rubber, polymer intermediates, etc. In 2018, the global output of ethylene was about 170 million tons, and its output is an important standard for measuring the development level of the country’s petrochemical industry. One is known as the "mother of petrochemical industry". Acetylene is often used for lighting, burning to produce high temperature to cut and weld metal; at the same time as the basic raw material to prepare acetaldehyde, acetic acid, synthetic fiber, synthetic rubber, etc. Ethylene is mainly separated from petroleum cracked gas. In the process of further separating and obtaining polymerization grade ethylene (acetylene content less than 40ppm), the presence of a small amount of acetylene will poison the catalyst used in the ethylene polymerization process and shorten the service life of the catalyst. At the same time, the formation of by-products reduces the quality of the polyethylene produced. In addition, acetylene will react with metals to form metal acetylene compounds, which hinder gas flow and even cause explosions. Therefore, traces of acetylene need to be removed from the ethylene-acetylene mixture.
目前，常见的乙烯乙炔的分离方法主要有选择性加氢、溶剂吸收、深冷分离以及吸附分离等。选择性加氢法根据加氢步骤在分离流程中的位置可分为前加氢和后加氢两种。前者如申请号为CN201611247546.2的中国专利，将前脱乙烷前加氢工艺中的塔顶流出物进入加氢反应器进行选择加氢，以脱除其中的炔烃和二烯烃；后加氢如申请号为CN201511032200.6的中国专利，将来自脱乙烷塔的塔顶流出物进入绝热反应器进行选择加氢，以脱除其中的乙炔。但仍存在反应过程中乙炔难以完全除去，同时产生乙烷副产物，催化剂易中毒失效等问题。溶剂吸收法代表性有美国AET公司的Mehra工艺，使用N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、碳酸丙烯酯等为吸收剂，但该方法存在有机溶剂损耗严重，效率低，能耗高的问题。由Air Products公司和Mobil公司共同开发的深冷分离技术应 用于液化催化裂化工艺，乙烯收率可达90％～98％，流程复杂，成本高。At present, the common separation methods of ethylene acetylene mainly include selective hydrogenation, solvent absorption, cryogenic separation, and adsorption separation. The selective hydrogenation method can be divided into pre-hydrogenation and post-hydrogenation according to the position of the hydrogenation step in the separation process. For the former, such as the Chinese patent with application number CN201611247546.2, the overhead effluent from the pre-deethane pre-hydrogenation process enters the hydrogenation reactor for selective hydrogenation to remove alkynes and dienes; For hydrogen, such as the Chinese patent application number CN201511032200.6, the overhead effluent from the de-ethanizer enters an adiabatic reactor for selective hydrogenation to remove acetylene. However, during the reaction process, acetylene is difficult to completely remove, and at the same time, ethane by-products are produced, and the catalyst is prone to poisoning and becoming invalid. The solvent absorption method is representative of the Mehra process of American AET Company, which uses N-methylpyrrolidone (NMP), dimethylformamide (DMF), propylene carbonate, etc. as absorbents, but this method has serious organic solvent loss and efficiency. The problem of low energy consumption. The cryogenic separation technology jointly developed by Air Products and Mobil is applied to the liquefaction catalytic cracking process. The ethylene yield can reach 90% to 98%, the process is complicated, and the cost is high.
传统分子筛材料，如介孔分子筛SBA-15，在30℃，1atm下，对乙炔具有1.55mmol/g的吸附量，但乙炔/乙烯的选择性很低，仅为1.8。普通的金属-有机框架材料应用于乙炔/乙烯的分离存在着高容量和高选择性无法兼顾的问题，如具有开放金属位点的大孔径材料Fe-MOF-74，在318K，1atm时，对乙炔的吸附量可达到6.1mmol/g，虽然对于乙炔具有高吸附量，但乙炔/乙烯的选择性只有2.0(Bloch E D,Queen W L,Krishna R,et al.Hydrocarbon separations in a metal-organic framework with open iron(II)coordination sites[J].Science,2012,335(6076):1606-1610)。而氨基功能化的金属-有机框架材料UTSA-100虽然对乙炔/乙烯的选择性可以达到10.8，但在296K，1atm时，对乙炔的吸附量为4.2mmol/g(Hu T L,Wang H L,Li B,et al.Microporous metal-organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures[J].Nature Communications,2015,6.7328)。Traditional molecular sieve materials, such as mesoporous molecular sieve SBA-15, have an adsorption capacity of 1.55 mmol/g for acetylene at 30°C and 1 atm, but the selectivity of acetylene/ethylene is very low, only 1.8. Ordinary metal-organic framework materials used in the separation of acetylene/ethylene have the problems of high capacity and high selectivity. For example, Fe-MOF-74, a large pore material with open metal sites, is suitable The adsorption capacity of acetylene can reach 6.1mmol/g. Although it has a high adsorption capacity for acetylene, the selectivity of acetylene/ethylene is only 2.0 (Bloch E D, Queen W L, Krishna R, et al. Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites[J].Science,2012,335(6076):1606-1610). Although the amino-functionalized metal-organic framework material UTSA-100 has a selectivity of 10.8 for acetylene/ethylene, its adsorption capacity for acetylene is 4.2mmol/g at 296K and 1atm (Hu T L, Wang H L) ,Li B,et al. Microporous metal-organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures[J]. Nature Communications, 2015, 6.7328).
Rui-Biao Lin等人报道了一种[Zn(dps) 2(SiF 6)]材料(UTSA-300a)，其中dps为4,4’-二吡啶硫醚，可选择性吸附乙炔，进而可用于分离乙炔/乙烯气体(Lin R B,Li L,Wu H,et al.Optimized Separation of Acetylene from Carbon Dioxide and Ethylene in a Microporous Material[J].Journal of the American Chemical Society,2017,139,8022-8028)。从该文献的Figure S16可知，常温(298K)下UTSA-300a对乙炔的吸附需要一定的压力条件(约150～200mmHg乙炔压力)，可见其对乙炔气体的吸附条件较为苛刻，需要混合气体中具有较高分压的乙炔才可实现对乙炔的吸附，限制了该材料对混合气体中低含量乙炔(低乙炔分压)的吸附分离应用。 Rui-Biao Lin et al. reported a [Zn(dps) 2 (SiF 6 )] material (UTSA-300a), where dps is 4,4'-dipyridine sulfide, which can selectively adsorb acetylene and can be used for Separation of acetylene/ethylene gas (Lin RB, Li L, Wu H, et al. Optimized Separation of Acetylene from Carbon Dioxide and Ethylene in a Microporous Material[J].Journal of the American Chemical Society,2017,139,8022-8028) . It can be seen from Figure S16 of the document that the adsorption of acetylene by UTSA-300a at room temperature (298K) requires a certain pressure condition (about 150-200mmHg acetylene pressure). It can be seen that the adsorption conditions for acetylene gas are relatively harsh, and the mixed gas needs to have Only higher partial pressure of acetylene can achieve the adsorption of acetylene, which limits the application of this material to the adsorption and separation of low-content acetylene (low acetylene partial pressure) in the mixed gas.
因此，亟需开发一种适用范围更广、可常温吸附分离痕量乙炔的乙炔/乙烯分离材料和分离方法。Therefore, there is an urgent need to develop an acetylene/ethylene separation material and separation method that has a wider application range and can adsorb and separate trace amounts of acetylene at room temperature.
发明内容Summary of the invention
针对本领域存在的不足之处，本发明提供了一种用于吸附分离乙炔乙烯的层状含氟金属-有机框架材料，该材料具有永久的三维孔道，对乙炔具有高选择性和高容量，特别适用于痕量乙炔的吸附分离，且稳定性好，制备方法简单，制备成本低廉。In view of the shortcomings in the field, the present invention provides a layered fluorine-containing metal-organic framework material for the adsorption and separation of acetylene and ethylene. The material has permanent three-dimensional pores and has high selectivity and high capacity for acetylene. It is especially suitable for the adsorption and separation of trace acetylene, with good stability, simple preparation method and low preparation cost.
一种用于吸附分离乙炔乙烯的层状含氟金属-有机框架材料，结构通式为ML 2A，其中M为金属离子，L为折线型有机配体，A为无机含氟阴离子，金属离子M与折线型有机配体L和无机含氟阴离子A通过配位键桥联形成具有一维孔道的二维网络，相邻二维网络通过超分子作用堆积形成具有永久三维贯穿孔道的层状三维结构； A layered fluorine-containing metal-organic framework material for the adsorption and separation of acetylene ethylene. The general structural formula is ML 2 A, where M is a metal ion, L is a broken-line organic ligand, A is an inorganic fluorine-containing anion, and a metal ion M is bridged with the broken-line organic ligand L and inorganic fluorine-containing anion A to form a two-dimensional network with one-dimensional pores through coordination bonds, and adjacent two-dimensional networks are stacked by supramolecular interaction to form a layered three-dimensional network with permanent three-dimensional through-holes. structure;
所述金属离子M为Cu 2+、Fe 2+、Co 2+、Ni 2+、Zn 2+中的至少一种； The metal ion M is at least one of Cu 2+ , Fe 2+ , Co 2+ , Ni 2+ , and Zn 2+;
所述折线型有机配体L为4,4’-二吡啶亚砜、4,4’-二吡啶砜中的至少一种，结构式分别如下式(I)、(II)所示：The polyline-type organic ligand L is at least one of 4,4'-dipyridine sulfoxide and 4,4'-dipyridine sulfone, and the structural formulas are respectively shown in the following formulas (I) and (II):
Figure PCTCN2021075162-appb-000001
Figure PCTCN2021075162-appb-000001
所述折线型有机配体L结构中含有的亚砜或砜基官能团既有利于获得永久的三维孔道，又有利于增强材料与气体分子的相互作用。The sulfoxide or sulfone functional group contained in the polyline-type organic ligand L structure not only helps to obtain permanent three-dimensional pores, but also helps to enhance the interaction between the material and the gas molecule.
所述无机含氟阴离子A为SiF 6 2-、GeF 6 2-、ZrF 6 2-、SnF 6 2-、TiF 6 2-、NbOF 5 2-、WO 2F 4 2-、MoO 2F 4 2-中的至少一种。 The inorganic fluorine-containing anion A is SiF 6 2- , GeF 6 2- , ZrF 6 2- , SnF 6 2- , TiF 6 2- , NbOF 5 2- , WO 2 F 4 2- , MoO 2 F 4 2 -At least one of.
所述层状含氟金属-有机框架材料具有一种永久的三维贯穿孔道，通过改变无机含氟阴离子、有机配体和金属离子种类，可以精准调节该材料平均孔径的大小。优选地，所述层状含氟金属-有机框架材料的平均孔径为
Figure PCTCN2021075162-appb-000002
The layered fluorine-containing metal-organic framework material has a permanent three-dimensional through-hole channel, and the average pore size of the material can be precisely adjusted by changing the types of inorganic fluorine-containing anions, organic ligands and metal ions. Preferably, the average pore diameter of the layered fluorine-containing metal-organic frame material is
Figure PCTCN2021075162-appb-000002
作为优选，所述金属离子M为Cu 2+、Ni 2+中的至少一种； Preferably, the metal ion M is at least one of Cu 2+ and Ni 2+;
所述折线型有机配体L为4,4’-二吡啶砜；The polyline-type organic ligand L is 4,4'-dipyridylsulfone;
所述无机含氟阴离子A为SiF 6 2-、GeF 6 2-、TiF 6 2-、NbOF 5 2-中的至少一种。 The inorganic fluorine-containing anion A is at least one of SiF 6 2- , GeF 6 2- , TiF 6 2- , and NbOF 5 2-.
上述优选组合得到的层状含氟金属-有机框架材料更有利于吸附分离 乙炔乙烯，低浓度乙炔的吸附容量和选择性更高。The layered fluorine-containing metal-organic framework material obtained by the above-mentioned preferred combination is more conducive to the adsorption and separation of ethylene acetylene, and the adsorption capacity and selectivity of low-concentration acetylene are higher.
在一优选例中，金属离子M是Cu 2+，有机配体是4,4’-二吡啶砜，无机含氟阴离子是SiF 6 2-离子。这种特别的层状含氟金属-有机框架材料的化学式为Cu(4,4'-dipyridylsulfone) 2SiF 6。 In a preferred example, the metal ion M is Cu 2+ , the organic ligand is 4,4'-dipyridylsulfone, and the inorganic fluorine-containing anion is SiF 6 2- ion. The chemical formula of this special layered fluorine-containing metal-organic framework material is Cu(4,4'-dipyridylsulfone) 2 SiF 6 .
在另一优选例中，金属离子M是Cu 2+，有机配体是4,4’-二吡啶砜，无机含氟阴离子是TiF 6 2-离子。这种特别的层状含氟金属-有机框架材料的化学式为Cu(4,4'-dipyridylsulfone) 2TiF 6。 In another preferred example, the metal ion M is Cu 2+ , the organic ligand is 4,4'-dipyridylsulfone, and the inorganic fluorine-containing anion is TiF 6 2- ion. The chemical formula of this special layered fluorine-containing metal-organic framework material is Cu(4,4'-dipyridylsulfone) 2 TiF 6 .
在另一优选例中，金属离子M是Cu 2+，有机配体是4,4’-二吡啶砜，无机含氟阴离子是NbOF 5 2-离子。这种特别的层状含氟金属-有机框架材料可以被称为Cu(4,4'-dipyridylsulfone) 2NbOF 5。 In another preferred example, the metal ion M is Cu 2+ , the organic ligand is 4,4'-dipyridylsulfone, and the inorganic fluorine-containing anion is NbOF 5 2- ion. This special layered fluorine-containing metal-organic framework material can be called Cu(4,4'-dipyridylsulfone) 2 NbOF 5 .
在另一优选例中，金属离子M是Ni 2+，有机配体是4,4’-二吡啶砜，无机含氟阴离子是TiF 6 2-离子。这种特别的层状含氟金属-有机框架材料可以被称为Ni(4,4'-dipyridylsulfone) 2TiF 6。 In another preferred example, the metal ion M is Ni 2+ , the organic ligand is 4,4'-dipyridylsulfone, and the inorganic fluorine-containing anion is TiF 6 2- ion. This special layered fluorine-containing metal-organic framework material can be called Ni(4,4'-dipyridylsulfone) 2 TiF 6 .
在另一优选例中，金属离子M是Ni 2+，有机配体是4,4’-二吡啶砜，无机含氟阴离子是NbOF 5 2-离子。这种特别的层状含氟金属-有机框架材料可以被称为Ni(4,4'-dipyridylsulfone) 2NbOF 5。 In another preferred example, the metal ion M is Ni 2+ , the organic ligand is 4,4'-dipyridylsulfone, and the inorganic fluorine-containing anion is NbOF 5 2- ion. This special layered fluorine-containing metal-organic framework material can be called Ni(4,4'-dipyridylsulfone) 2 NbOF 5 .
在另一优选例中，金属离子M是Zn 2+，有机配体是4,4’-二吡啶砜，无机含氟阴离子是NbOF 5 2-离子。这种特别的层状含氟金属-有机框架材料可以被称为Zn(4,4'-dipyridylsulfone) 2NbOF 5。 In another preferred example, the metal ion M is Zn 2+ , the organic ligand is 4,4'-dipyridylsulfone, and the inorganic fluorine-containing anion is NbOF 5 2- ion. This special layered fluorine-containing metal-organic framework material can be called Zn(4,4'-dipyridylsulfone) 2 NbOF 5 .
在另一优选例中，金属离子M是Cu 2+，有机配体是4,4’-二吡啶亚砜，无机含氟阴离子是MoO 2F 4 2-离子。这种特别的层状含氟金属-有机框架材料可以被称为Cu(4,4'-dipyridylsulfoxide) 2MoO 2F 4。 In another preferred example, the metal ion M is Cu 2+ , the organic ligand is 4,4'-dipyridine sulfoxide, and the inorganic fluorine-containing anion is MoO 2 F 4 2- ion. This special layered fluorine-containing metal-organic framework material can be called Cu(4,4'-dipyridylsulfoxide) 2 MoO 2 F 4 .
在另一优选例中，金属离子M是Cu 2+，有机配体是4,4’-二吡啶亚砜，无机含氟阴离子是NbOF 5 2-离子。这种特别的层状含氟金属-有机框架材料可以被称为Cu(4,4'-dipyridylsulfoxide) 2NbOF 5。 In another preferred example, the metal ion M is Cu 2+ , the organic ligand is 4,4'-dipyridine sulfoxide, and the inorganic fluorine-containing anion is NbOF 5 2- ion. This special layered fluorine-containing metal-organic framework material can be called Cu(4,4'-dipyridylsulfoxide) 2 NbOF 5 .
本发明的层状含氟金属-有机框架材料稳定性好、制备方法简单、制备成本低廉，具有优异的乙炔捕捉能力和乙炔/乙烯选择性分离性能，尤其在常温下对痕量乙炔的脱除效果显著，在气体吸附、储存与分离等领域具有良好的工业应用前景。The layered fluorine-containing metal-organic framework material of the present invention has good stability, simple preparation method, low preparation cost, excellent acetylene capture capacity and acetylene/ethylene selective separation performance, especially for the removal of trace amounts of acetylene at room temperature The effect is remarkable, and it has good industrial application prospects in the fields of gas adsorption, storage and separation.
本发明还提供了所述的层状含氟金属-有机框架材料的制备方法，包括步骤：The present invention also provides a method for preparing the layered fluorine-containing metal-organic framework material, which includes the steps:
(1)将金属离子无机盐、无机含氟阴离子化合物按配比溶于有机溶剂、去离子水或去离子水和有机溶剂的混合液中，得金属离子-无机含氟阴离子溶液；将有机配体按配比溶于有机溶剂或去离子水和有机溶剂的混合液中，得有机配体溶液；(1) The metal ion inorganic salt and inorganic fluorine-containing anion compound are dissolved in an organic solvent, deionized water or a mixture of deionized water and organic solvent according to the proportion to obtain a metal ion-inorganic fluorine-containing anion solution; the organic ligand Dissolve in an organic solvent or a mixture of deionized water and an organic solvent according to the ratio to obtain an organic ligand solution;
(2)将有机配体溶液滴加在金属离子-无机含氟阴离子溶液上方，利用界面扩散法制备得金属-阴离子-有机框架材料；或者直接将有机配体溶液和金属离子-无机含氟阴离子溶液混合，利用溶剂热法制备得金属-阴离子-有机框架材料；或者将有机配体溶液和金属离子-无机含氟阴离子溶液直接混合室温搅拌制备得金属-阴离子-有机框架材料；(2) Drop the organic ligand solution on top of the metal ion-inorganic fluorine-containing anion solution, and use the interface diffusion method to prepare the metal-anion-organic framework material; or directly combine the organic ligand solution and the metal ion-inorganic fluorine-containing anion solution Solution mixing, the metal-anion-organic framework material is prepared by solvothermal method; or the organic ligand solution and the metal ion-inorganic fluorine-containing anion solution are directly mixed and stirred at room temperature to prepare the metal-anion-organic framework material;
(3)所得金属-阴离子-有机框架材料经过滤、洗涤、干燥得所述层状含氟金属-有机框架材料。(3) The obtained metal-anion-organic framework material is filtered, washed, and dried to obtain the layered fluorine-containing metal-organic framework material.
作为优选，所述金属离子无机盐为金属离子M的硝酸盐、氯化盐、乙酸盐、碳酸盐、硫酸盐、高氯酸盐、四氟硼酸盐中的至少一种。Preferably, the metal ion inorganic salt is at least one of metal ion M nitrate, chloride, acetate, carbonate, sulfate, perchlorate, and tetrafluoroborate.
作为优选，所述有机溶剂为甲醇、乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、乙腈、丙酮、氯仿、二氯甲烷、二甲亚砜、乙二醇、丙三醇中的至少一种。Preferably, the organic solvent is methanol, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, acetone, chloroform, dichloromethane, dimethylformamide At least one of sulfoxide, ethylene glycol, and glycerol.
作为优选，所述金属离子无机盐、无机含氟阴离子化合物、有机配体的摩尔比为1:0.5～3:0.5～5。Preferably, the molar ratio of the metal ion inorganic salt, the inorganic fluorine-containing anion compound, and the organic ligand is 1:0.5-3:0.5-5.
作为优选，所述界面扩散法和溶剂热法的反应温度均为10～120℃，反应时间均为1～72h。进一步优选，所述溶剂热法的反应温度为60～90℃反应时间为12～24h。Preferably, the reaction temperature of the interface diffusion method and the solvothermal method are both 10-120°C, and the reaction time is both 1-72h. More preferably, the reaction temperature of the solvothermal method is 60-90°C and the reaction time is 12-24h.
作为优选，所述洗涤过程为甲醇洗涤抽滤后，浸泡于甲醇中24～72h；Preferably, the washing process is methanol washing and suction filtration, followed by soaking in methanol for 24 to 72 hours;
所述干燥过程为：利用真空脱附、流动气体(如N 2、He、Ar等)吹扫，温度为25～120℃，时间为6～72h。 The drying process is: using vacuum desorption, purging with flowing gas (such as N 2 , He, Ar, etc.), the temperature is 25-120° C., and the time is 6-72 h.
本发明方法制备得到的层状含氟金属-有机框架材料颗粒形状规则，具有很高的水、热稳定性。The layered fluorine-containing metal-organic framework material particles prepared by the method of the invention have regular shapes and high water and thermal stability.
本发明还提供了所述的层状含氟金属-有机框架材料在吸附分离乙炔乙烯中的应用，以所述的层状含氟金属-有机框架材料为吸附剂，与含乙炔和乙烯的气体混合物接触进行吸附分离。The present invention also provides the application of the layered fluorine-containing metal-organic framework material in the adsorption and separation of acetylene and ethylene. The layered fluorine-containing metal-organic framework material is used as an adsorbent, and the gas containing acetylene and ethylene is used as an adsorbent. The mixture is contacted for adsorption separation.
所述层状含氟金属-有机框架材料的三维贯穿孔道的形状和大小与乙炔分子相似，孔道内部具有高密度的、带负电荷的氟原子，可与乙炔分子 发生很强的特异性氢键作用，在常温、低压(乙炔分压不大于0.2bar)下即可实现对乙炔的高容量优先吸附，远高于对乙烯的吸附容量，从而获得很高的乙炔/乙烯分离选择性。该材料在低压下对乙炔的吸附容量高于所有现有材料，选择性高于绝大多数现有材料。The shape and size of the three-dimensional through pores of the layered fluorine-containing metal-organic framework material are similar to those of acetylene molecules, and the pores have high-density and negatively charged fluorine atoms, which can form strong specific hydrogen bonds with the acetylene molecules. Function, under normal temperature and low pressure (the partial pressure of acetylene is not more than 0.2bar), the high capacity and preferential adsorption of acetylene can be realized, which is much higher than the adsorption capacity of ethylene, so as to obtain high acetylene/ethylene separation selectivity. The adsorption capacity of this material for acetylene under low pressure is higher than that of all existing materials, and the selectivity is higher than that of most existing materials.
作为优选，所述应用具体包括如下步骤：将脱溶剂后的层状含氟金属-有机框架材料样品装填入吸附柱内；将含乙炔和乙烯的气体混合物通入吸附柱。乙烯与吸附剂相互作用力较弱，较快地从吸附柱尾端流出，而乙炔与吸附剂相互作用力较强，待吸附达到饱和后缓慢从吸附柱尾端流出。由于材料对两种气体的相互作用力不同，以此实现气体混合物中乙炔和乙烯的有效分离。Preferably, the application specifically includes the following steps: loading the desolventized layered fluorine-containing metal-organic framework material sample into the adsorption column; passing the gas mixture containing acetylene and ethylene into the adsorption column. Ethylene has a weak interaction force with the adsorbent and flows out from the end of the adsorption column faster, while acetylene has a strong interaction force with the adsorbent, and slowly flows out from the end of the adsorption column after the adsorption reaches saturation. Due to the different interaction forces of the materials on the two gases, the effective separation of acetylene and ethylene in the gas mixture can be achieved.
作为优选，所述气体混合物中乙炔与乙烯的体积比为0.05:99.95至10:90。Preferably, the volume ratio of acetylene to ethylene in the gas mixture is 0.05:99.95 to 10:90.
作为优选，所述吸附分离的温度为-5～60℃，所述气体混合物的压力为0.5～5bar。进一步优选，所述吸附分离的温度为20～60℃，所述气体混合物的压力为0.5～2bar。再进一步优选，所述吸附分离的温度为25～25℃，所述气体混合物的压力为常压。在上述优选条件下能够更好地兼顾乙炔吸附容量、选择性、吸附速率、能耗等各方面因素。Preferably, the temperature of the adsorption separation is -5-60°C, and the pressure of the gas mixture is 0.5-5 bar. Further preferably, the temperature of the adsorption separation is 20-60°C, and the pressure of the gas mixture is 0.5-2 bar. Still further preferably, the temperature of the adsorption separation is 25-25°C, and the pressure of the gas mixture is normal pressure. Under the above-mentioned preferred conditions, various factors such as acetylene adsorption capacity, selectivity, adsorption rate, and energy consumption can be better considered.
所述的气体混合物中不仅限于含有乙炔和乙烯，也可以含有其它如水蒸气、二氧化碳、氩气、氮气、氧气、甲烷和氦气等气体。The said gas mixture is not limited to containing acetylene and ethylene, but can also contain other gases such as water vapor, carbon dioxide, argon, nitrogen, oxygen, methane and helium.
所述层状含氟金属-有机框架材料选择性吸附乙炔后，脱附即得乙炔。After the layered fluorine-containing metal-organic framework material selectively adsorbs acetylene, acetylene is obtained by desorption.
所述脱附条件为：真空或惰性气体(如氦气、氮气等)气氛，脱附温度25～120℃。同时，可实现层状含氟金属-有机框架材料的再生。加热温度过高会导致吸附剂结构破坏；温度过低，吸附剂内残留的吸附质将无法全部脱除。The desorption conditions are: vacuum or inert gas (such as helium, nitrogen, etc.) atmosphere, and the desorption temperature is 25-120°C. At the same time, the regeneration of layered fluorine-containing metal-organic framework materials can be realized. If the heating temperature is too high, the structure of the adsorbent will be destroyed; if the temperature is too low, the adsorbate remaining in the adsorbent will not be completely removed.
作为优选，所述脱附温度为40～80℃。Preferably, the desorption temperature is 40-80°C.
本发明与现有技术相比，主要优点包括：Compared with the prior art, the main advantages of the present invention include:
(1)本发明中的层状含氟金属-有机框架材料具有水、热稳定性好，制备方法简单和制备成本低廉等突出优点，具有很好的工业应用前景；(1) The layered fluorine-containing metal-organic framework material of the present invention has outstanding advantages such as good water and thermal stability, simple preparation method and low preparation cost, and has good industrial application prospects;
(2)本发明中的层状含氟金属-有机框架材料相比传统吸附剂，具有与乙炔分子作用力强、在低乙炔分压下对乙炔吸附容量高、对乙炔/乙烯选择性高、可循环利用等优势；(2) Compared with the traditional adsorbent, the layered fluorine-containing metal-organic framework material of the present invention has a strong force with acetylene molecules, a high adsorption capacity for acetylene under low acetylene partial pressure, and a high selectivity for acetylene/ethylene. Recyclable and other advantages;
(3)提供了一种层状含氟金属-有机框架材料吸附分离乙炔乙烯的方法，通过精准调控材料的孔结构和孔径，提高对乙炔分子的特异性识别能力，进而实现乙炔与乙烯两者的高选择性分离；(3) A method for the adsorption and separation of acetylene and ethylene by layered fluorine-containing metal-organic framework materials is provided. Through precise control of the pore structure and pore size of the material, the specific recognition ability of acetylene molecules is improved, thereby achieving both acetylene and ethylene High selectivity separation;
(4)本方法可根据工业需要得到高纯度的乙烯产品，纯度可达99.9999％以上；(4) This method can obtain high-purity ethylene products according to industrial needs, and the purity can reach more than 99.9999%;
(5)本发明提供的分离方法与传统溶剂吸收、萃取精馏和催化加氢技术相比，具有能耗低，条件温和，设备投资小等突出优点。(5) Compared with traditional solvent absorption, extractive distillation and catalytic hydrogenation technologies, the separation method provided by the present invention has outstanding advantages such as low energy consumption, mild conditions, and small equipment investment.
附图说明Description of the drawings
图1为实施例1得到的层状含氟金属-有机框架材料的晶体结构示意图；1 is a schematic diagram of the crystal structure of the layered fluorine-containing metal-organic framework material obtained in Example 1;
图2A、2B分别为实施例1所述的层状含氟金属-有机框架材料298K下对乙炔、乙烯的吸附等温线图及乙炔、乙烯的吸附热图；2A and 2B are respectively the adsorption isotherms of acetylene and ethylene and the adsorption heat maps of acetylene and ethylene under the layered fluorine-containing metal-organic framework material described in Example 1 at 298K;
图3为实施例1所述的层状含氟金属-有机框架材料的PXRD数据图；3 is a PXRD data diagram of the layered fluorine-containing metal-organic framework material described in Example 1;
图4为实施例2所述的层状含氟金属-有机框架材料的乙炔乙烯混合气体的穿透曲线图，纵坐标中C为出口气中各组分浓度，C 0为原料气初始浓度； 4 is the penetration curve diagram of the acetylene ethylene mixed gas of the layered fluorine-containing metal-organic framework material described in Example 2. In the ordinate, C is the concentration of each component in the outlet gas, and C 0 is the initial concentration of the raw gas;
图5为实施例5得到的层状含氟金属-有机框架材料的晶体结构示意图；5 is a schematic diagram of the crystal structure of the layered fluorine-containing metal-organic framework material obtained in Example 5;
图6A、6B分别为实施例5所述的层状含氟金属-有机框架材料298K下对乙炔、乙烯的吸附等温线图及乙炔、乙烯的吸附热图；6A and 6B are respectively the adsorption isotherm of acetylene and ethylene and the adsorption heat map of acetylene and ethylene at 298K of the layered fluorine-containing metal-organic framework material described in Example 5;
图7为实施例5所述的层状含氟金属-有机框架材料的PXRD数据图；7 is a PXRD data diagram of the layered fluorine-containing metal-organic framework material described in Example 5;
图8为实施例6所述的层状含氟金属-有机框架材料的乙炔乙烯混合气体的穿透曲线图，纵坐标中C为出口气中各组分浓度，C 0为原料气初始浓度； 8 is the penetration curve diagram of the acetylene ethylene mixed gas of the layered fluorine-containing metal-organic framework material described in Example 6, in the ordinate, C is the concentration of each component in the outlet gas, and C 0 is the initial concentration of the raw material gas;
图9为实施例8得到的层状含氟金属-有机框架材料的晶体结构示意图；9 is a schematic diagram of the crystal structure of the layered fluorine-containing metal-organic framework material obtained in Example 8;
图10为实施例8所述的层状含氟金属-有机框架材料298K下对乙炔、乙烯的吸附等温线图；10 is the adsorption isotherm diagram of the layered fluorine-containing metal-organic framework material described in Example 8 for acetylene and ethylene at 298K;
图11为实施例8所述的层状含氟金属-有机框架材料的PXRD数据图；11 is a PXRD data diagram of the layered fluorine-containing metal-organic framework material described in Example 8;
图12为实施例10所述的层状含氟金属-有机框架材料298K下对乙 炔的吸附等温线图；Fig. 12 is a diagram showing the adsorption isotherm of the layered fluorine-containing metal-organic framework material described in Example 10 for acetylene at 298K;
图13为实施例12所述的层状含氟金属-有机框架材料298K下对乙炔的吸附等温线图；13 is a diagram showing the adsorption isotherm of the layered fluorine-containing metal-organic framework material described in Example 12 for acetylene at 298K;
图14为实施例15得到的层状含氟金属-有机框架材料的PXRD数据图；14 is a PXRD data chart of the layered fluorine-containing metal-organic framework material obtained in Example 15;
图15为实施例17得到的层状含氟金属-有机框架材料的PXRD数据图。15 is a PXRD data chart of the layered fluorine-containing metal-organic framework material obtained in Example 17.
具体实施方式Detailed ways
下面结合附图及具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。The present invention will be further described below in conjunction with the drawings and specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. The operating methods without specific conditions in the following examples are usually in accordance with conventional conditions or in accordance with the conditions recommended by the manufacturer.
在以下实施例中，使用以下单晶X射线衍射仪获得单晶X射线结构：配备有CMOS检测器和1uS微焦Cu X射线源的Bruker Quest衍射仪。In the following examples, the following single crystal X-ray diffractometer is used to obtain a single crystal X-ray structure: a Bruker Quest diffractometer equipped with a CMOS detector and a 1uS micro-focus Cu X-ray source.
使用以下粉末衍射仪验证样品的纯度：使用Cu
Figure PCTCN2021075162-appb-000003
辐射的SHIMADZU XRD-6000。 Use the following powder diffractometer to verify the purity of the sample: Use Cu
Figure PCTCN2021075162-appb-000003
Radiant SHIMADZU XRD-6000.
使用以下气体吸附仪器收集吸附等温线：ASAP 2460 Analyzer(Micromeritics)。Use the following gas adsorption equipment to collect adsorption isotherms: ASAP 2460 Analyzer (Micromeritics).
使用以下脱气仪器将样品脱气(用于活化)：Micromeritics Smart VacPrep气体吸附样品制备装置。Use the following degassing instrument to degas the sample (for activation): Micromeritics Smart VacPrep gas adsorption sample preparation device.
实施例1Example 1
采用室温搅拌法合成方法，将0.5mmol Cu(BF 4) 2和0.5mmol(NH 4) 2TiF 6溶于去离子水，1mmol 4,4’-二吡啶砜溶解于无水甲醇中，两者混合，25℃反应24h后得到晶体，所得晶体过滤、甲醇洗涤、干燥，得到Cu(4,4'-dipyridylsulfone) 2TiF 6。 The room temperature stirring method was used to synthesize 0.5mmol Cu(BF 4 ) 2 and 0.5mmol(NH 4 ) 2 TiF 6 in deionized water, and 1mmol 4,4'-dipyridylsulfone was dissolved in anhydrous methanol. After mixing and reacting at 25°C for 24 hours, crystals are obtained. The crystals obtained are filtered, washed with methanol, and dried to obtain Cu(4,4'-dipyridylsulfone) 2 TiF 6 .
1、Cu(4,4'-dipyridylsulfone) 2TiF 6的结构 1. The structure of Cu(4,4'-dipyridylsulfone) 2 TiF 6
Cu(4,4'-dipyridylsulfone) 2TiF 6是具有层状三维结构的金属-有机框架材料。晶体结构如图1所示，金属铜离子与有机配体4,4’-二吡啶砜形成拟一维链状结构(ab平面)，再和无机含氟阴离子TiF 6 2-在c轴方向上通过配位键桥联形成具有一维孔道的二维网络，相邻二维网络通过超分子作用堆积 形成具有永久的三维贯穿孔道的层状三维结构。如图1A所示，该材料具有相互垂直的层间孔道以及层内孔道。图1B所示，沿c轴方向的层内孔道，开口尺寸为
Figure PCTCN2021075162-appb-000004
图1C所示的是沿a轴方向的层间孔道，开口尺寸为
Figure PCTCN2021075162-appb-000005
无机含氟阴离子TiF 6 2-为层内及层间三维贯穿孔道提供了带负电荷的作用位点，加强了与C 2H 2的相互作用。 Cu(4,4'-dipyridylsulfone) 2 TiF 6 is a metal-organic framework material with a layered three-dimensional structure. The crystal structure is shown in Figure 1. The metal copper ion and the organic ligand 4,4'-dipyridylsulfone form a pseudo-one-dimensional chain structure (ab plane), and the inorganic fluorine-containing anion TiF 6 2- is in the c-axis direction. A two-dimensional network with one-dimensional pores is formed by bridging by coordination bonds, and adjacent two-dimensional networks are stacked by supramolecular action to form a layered three-dimensional structure with permanent three-dimensional through pores. As shown in Figure 1A, the material has interlayer pores and intralayer pores that are perpendicular to each other. As shown in Figure 1B, the intra-layer pores along the c-axis direction have an opening size of
Figure PCTCN2021075162-appb-000004
Figure 1C shows the interlayer channels along the a-axis, and the opening size is
Figure PCTCN2021075162-appb-000005
The inorganic fluorine-containing anion TiF 6 2- provides negatively charged action sites for the three-dimensional through-holes within and between the layers, and strengthens the interaction with C 2 H 2 .
2、Cu(4,4'-dipyridylsulfone) 2TiF 6的纯气体吸附研究 2. Cu(4,4'-dipyridylsulfone) 2 TiF 6 pure gas adsorption research
Cu(4,4'-dipyridylsulfone) 2TiF 6材料298K时对乙烯、乙炔的吸附等温线如图2A所示。Cu(4,4'-dipyridylsulfone) 2TiF 6对C 2H 2的吸附容量比C 2H 4大，特别是在低压区。在298K下，分别在0.01bar和1bar下测得C 2H 2的吸附量为2.96mmol/g和5.31mmol/g，在相同条件下，测得C 2H 4的吸附量仅为0.37mmol/g和2.76mmol/g。通过Virial方程，C 2H 2的吸附热Q st计算为65.3kJ/mol，远高于C 2H 4的35.9kJ/mol，如图2B所示。 The adsorption isotherm of ethylene and acetylene for Cu(4,4'-dipyridylsulfone) 2 TiF 6 at 298K is shown in Figure 2A. The adsorption capacity of Cu(4,4'-dipyridylsulfone) 2 TiF 6 for C 2 H 2 is larger than that of C 2 H 4 , especially in the low pressure area. At 298K, the adsorption capacity of C 2 H 2 measured at 0.01 bar and 1 bar was 2.96 mmol/g and 5.31 mmol/g. Under the same conditions, the measured adsorption capacity of C 2 H 4 was only 0.37 mmol/g. g and 2.76mmol/g. According to the Virial equation, the adsorption heat Q st of C 2 H 2 is calculated to be 65.3 kJ/mol, which is much higher than 35.9 kJ/mol of C 2 H 4 , as shown in Figure 2B.
3、粉末X射线衍射(PXRD)和稳定性数据3. Powder X-ray diffraction (PXRD) and stability data
通过将Cu(4,4'-dipyridylsulfone) 2TiF 6暴露在空气中和浸泡在水、pH＝1及pH＝12的水溶液中，持续7天，测试Cu(4,4'-dipyridylsulfone) 2TiF 6对空气、水及酸碱的稳定性。稳定性测试后样品的PXRD图与新合成的样品一致(见图3)，说明其结构对空气、水及酸碱都具有很好的稳定性。 By Cu (4,4'-dipyridylsulfone) 2 TiF 6 exposed to air and immersed in water, pH = 1 and the aqueous solution of pH = 12 for 7 days, the test Cu (4,4'-dipyridylsulfone) 2 TiF 6 Stability to air, water, acid and alkali. The PXRD pattern of the sample after the stability test is consistent with the newly synthesized sample (see Figure 3), indicating that its structure has good stability to air, water, acid and alkali.
实施例2Example 2
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例1所得Cu(4,4'-dipyridylsulfone) 2TiF 6材料填装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比1:99)混合气以1.25mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体。穿透曲线如图4所示。经测试，乙烯在48分钟穿透，乙炔在2200分钟才开始穿透，乙炔动态吸附量为1.9mmol/g。两种气体得到了有效的分离。该材料经5次吸附-再生循环，吸附性能仍然稳定。 The Cu(4,4'-dipyridylsulfone) 2 TiF 6 material obtained in Example 1 was packed into a 5 cm long adsorption column (inner diameter of 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of acetylene: ethylene (volume ratio 1:99) mixed gas was passed into the adsorption column at 1.25mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the tube. Exhaust from the column outlet. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas. The penetration curve is shown in Figure 4. After testing, ethylene penetrated in 48 minutes, and acetylene began to penetrate in 2200 minutes, and the dynamic adsorption capacity of acetylene was 1.9 mmol/g. The two gases are effectively separated. After 5 adsorption-regeneration cycles, the adsorption performance of this material is still stable.
实施例3Example 3
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例1所得Cu(4,4'-dipyridylsulfone) 2TiF 6材料填装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比10:90)混合气以1mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体。再生后吸附柱可循环使用。 The Cu(4,4'-dipyridylsulfone) 2 TiF 6 material obtained in Example 1 was packed into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the column. Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas. After regeneration, the adsorption column can be recycled.
实施例4Example 4
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例1所得Cu(4,4'-dipyridylsulfone) 2TiF 6材料填装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的水:乙炔:乙烯(体积比0.1:0.999:98.901)混合气以1mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC 2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体，再生后吸附柱可循环使用。 The Cu(4,4'-dipyridylsulfone) 2 TiF 6 material obtained in Example 1 was packed into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of water: acetylene: ethylene (volume ratio 0.1:0.999:98.901) mixed gas was passed into the adsorption column at 1mL/min at 25°C, and gas chromatograph (GC 2010Pro, SHIMADZU) with flame ionization detector (FID) was used. ) Monitor the exhaust gas from the outlet of the pipe string. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
实施例5Example 5
采用界面慢扩散方法，将溶有0.2mmol 4,4’-二吡啶砜的甲醇溶液缓慢滴加在溶有0.1mmol CuNbOF 5的DMF溶液上，25℃反应72h后过滤、甲醇洗涤、干燥，得到Cu(4,4'-dipyridylsulfone) 2NbOF 5材料。 Using the slow interface diffusion method, the methanol solution with 0.2mmol 4,4'-dipyridylsulfone was slowly dropped onto the DMF solution with 0.1mmol CuNbOF 5 , reacted at 25°C for 72h, filtered, washed with methanol, and dried to obtain Cu(4,4'-dipyridylsulfone) 2 NbOF 5 material.
1、Cu(4,4'-dipyridylsulfone) 2NbOF 5的结构 1. The structure of Cu(4,4'-dipyridylsulfone) 2 NbOF 5
Cu(4,4'-dipyridylsulfone) 2NbOF 5的晶体结构如图5所示。 The crystal structure of Cu(4,4'-dipyridylsulfone) 2 NbOF 5 is shown in Figure 5.
Cu(4,4'-dipyridylsulfone) 2NbOF 5是具有层状三维结构的金属-有机框架材料。金属铜离子与折线形有机配体4,4’-二吡啶砜形成拟一维链状结构，无机含氟阴离子NbOF 5 2-在垂直方向上通过配位键桥联形成具有一维孔道的二维网络，相邻二维网络通过超分子作用堆积形成具有三维贯穿孔道的层状三维结构。该材料层内孔道的开口尺寸为
Figure PCTCN2021075162-appb-000006
层间孔道的开口尺寸为
Figure PCTCN2021075162-appb-000007
无机含氟阴离子NbOF 5 2-为层内及层间三维贯穿孔道提供了带负电荷的作用位点，加强了与C 2H 2的相互作用。 Cu(4,4'-dipyridylsulfone) 2 NbOF 5 is a metal-organic framework material with a layered three-dimensional structure. The metal copper ion and the broken-line organic ligand 4,4'-dipyridylsulfone form a pseudo-one-dimensional chain structure, and the inorganic fluorine-containing anion NbOF 5 2- is bridged by a coordination bond in the vertical direction to form a two-dimensional structure with one-dimensional pores. Two-dimensional network, adjacent two-dimensional networks are stacked by supramolecular action to form a layered three-dimensional structure with three-dimensional through-holes. The opening size of the pores in the material layer is
Figure PCTCN2021075162-appb-000006
The opening size of the interlayer channel is
Figure PCTCN2021075162-appb-000007
The inorganic fluorine-containing anion NbOF 5 2- provides negatively charged action sites for the three-dimensional through-holes in and between the layers, and strengthens the interaction with C 2 H 2 .
2、Cu(4,4'-dipyridylsulfone) 2NbOF 5的纯气体吸附研究 2. Cu(4,4'-dipyridylsulfone) 2 NbOF 5 pure gas adsorption study
Cu(4,4'-dipyridylsulfone) 2NbOF 5材料298K时对乙烯、乙炔的吸附等温线如图6A所示。Cu(4,4'-dipyridylsulfone) 2NbOF 5对C 2H 2的吸附容量比C 2H 4大，特别是在低压区。在298K下，分别在0.01bar和1bar下测得C 2H 2的吸附量为2.23mmol/g和4.69mmol/g。在相同条件下，测得C 2H 4的吸附量仅为0.18mmol/g和1.99mmol/g。通过Virial方程，C 2H 2的吸附热Q st计算为57.6kJ/mol，远高于C 2H 4的36.9kJ/mol，如图6B所示。 The adsorption isotherm of ethylene and acetylene for Cu(4,4'-dipyridylsulfone) 2 NbOF 5 at 298K is shown in Figure 6A. The adsorption capacity of Cu(4,4'-dipyridylsulfone) 2 NbOF 5 for C 2 H 2 is larger than that of C 2 H 4 , especially in the low pressure area. At 298K, the adsorption capacity of C 2 H 2 was 2.23 mmol/g and 4.69 mmol/g measured at 0.01 bar and 1 bar, respectively. Under the same conditions, the measured adsorption capacity of C 2 H 4 is only 0.18 mmol/g and 1.99 mmol/g. According to the Virial equation, the adsorption heat Q st of C 2 H 2 is calculated to be 57.6 kJ/mol, which is much higher than 36.9 kJ/mol of C 2 H 4 , as shown in Figure 6B.
3、粉末X射线衍射(PXRD)和稳定性数据3. Powder X-ray diffraction (PXRD) and stability data
通过将Cu(4,4'-dipyridylsulfone) 2NbOF 5暴露在空气中和浸泡在水，pH＝1及pH＝12的水溶液中，持续7天，测试Cu(4,4'-dipyridylsulfone) 2NbOF 5对空气、水及酸碱的稳定性。稳定性测试后样品的PXRD图与新合成的样品一致(见图7)，说明其结构对空气、水及酸碱都具有很好的稳定性。 By Cu (4,4'-dipyridylsulfone) 2 NbOF 5 and exposed to air immersed in water, pH = 1 and the aqueous solution of pH = 12 for 7 days, the test Cu (4,4'-dipyridylsulfone) 2 NbOF 5. Stability to air, water, acid and alkali. The PXRD pattern of the sample after the stability test is consistent with that of the newly synthesized sample (see Figure 7), indicating that its structure has good stability to air, water, acid and alkali.
实施例6Example 6
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例5所得Cu(4,4'-dipyridylsulfone) 2NbOF 5材料填装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比1:99)混合气以1.25mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体。穿透曲线如图8所示。经测试，乙烯在35分钟穿透，乙炔在1800分钟才开始穿透，乙炔动态吸附量为1.3mmol/g。两种气体得到了有效的分离。该材料经5次吸附-再生循环，吸附性能仍然稳定。 The Cu(4,4'-dipyridylsulfone) 2 NbOF 5 material obtained in Example 5 was packed into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of acetylene: ethylene (volume ratio 1:99) mixed gas was passed into the adsorption column at 1.25 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the tube. Exhaust from the column outlet. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas. The penetration curve is shown in Figure 8. After testing, ethylene penetrated in 35 minutes, acetylene began to penetrate in 1800 minutes, and the dynamic adsorption capacity of acetylene was 1.3 mmol/g. The two gases are effectively separated. After 5 adsorption-regeneration cycles, the adsorption performance of this material is still stable.
实施例7Example 7
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例5所得Cu(4,4'-dipyridylsulfone) 2NbOF 5材料填装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比10:90)混合气以1mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC 2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体，再生后吸附柱可循环使用。 The Cu(4,4'-dipyridylsulfone) 2 NbOF 5 material obtained in Example 5 was packed into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C. Hour. Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC 2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the tube. Exhaust from the column outlet. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
实施例8Example 8
采用溶剂热方法，将0.5mmol Cu(BF 4) 2和0.5mmol(NH 4) 2SiF 6溶于去离子水，1mmol 4,4’-二吡啶砜溶解于无水甲醇中，两者混合，65℃反应12h后得到晶体，所得晶体过滤、甲醇洗涤、干燥，得到Cu(4,4'-dipyridylsulfone) 2SiF 6材料。 Using solvothermal method, 0.5mmol Cu(BF 4 ) 2 and 0.5mmol(NH 4 ) 2 SiF 6 were dissolved in deionized water, 1mmol 4,4'-dipyridylsulfone was dissolved in anhydrous methanol, and the two were mixed. After reacting at 65°C for 12 hours, crystals were obtained. The crystals obtained were filtered, washed with methanol, and dried to obtain Cu(4,4'-dipyridylsulfone) 2 SiF 6 material.
1、Cu(4,4'-dipyridylsulfone) 2SiF 6的结构 1. The structure of Cu(4,4'-dipyridylsulfone) 2 SiF 6
Cu(4,4'-dipyridylsulfone) 2SiF 6的晶体结构如图9所示。 The crystal structure of Cu(4,4'-dipyridylsulfone) 2 SiF 6 is shown in FIG. 9.
Cu(4,4'-dipyridylsulfone) 2SiF 6是具有层状三维结构的金属-有机框架材料。金属铜离子与有机配体4,4’-二吡啶砜和无机含氟阴离子SiF 6 2-通过配位键桥联形成具有一维孔道的二维网络，相邻二维网络通过超分子作用堆积形成具有三维贯穿孔道的层状三维结构。该材料层内孔道的开口尺寸为
Figure PCTCN2021075162-appb-000008
层间孔道的开口尺寸为
Figure PCTCN2021075162-appb-000009
无机含氟阴离子SiF 6 2-为层内及层间三维贯穿孔道提供了带负电荷的作用位点，加强了与C 2H 2的相互作用。 Cu(4,4'-dipyridylsulfone) 2 SiF 6 is a metal-organic framework material with a layered three-dimensional structure. The metal copper ion and the organic ligand 4,4'-dipyridylsulfone and the inorganic fluorine-containing anion SiF 6 2- are bridged by coordination bonds to form a two-dimensional network with one-dimensional pores, and adjacent two-dimensional networks are stacked by supramolecular action A layered three-dimensional structure with three-dimensional through holes is formed. The opening size of the pores in the material layer is
Figure PCTCN2021075162-appb-000008
The opening size of the interlayer channel is
Figure PCTCN2021075162-appb-000009
The inorganic fluorine-containing anion SiF 6 2- provides negatively charged action sites for the three-dimensional through-holes within and between the layers, and strengthens the interaction with C 2 H 2 .
2、Cu(4,4'-dipyridylsulfone) 2SiF 6的纯气体吸附研究 2. Cu(4,4'-dipyridylsulfone) 2 SiF 6 pure gas adsorption research
Cu(4,4'-dipyridylsulfone) 2SiF 6材料298K时对乙烯、乙炔的吸附等温线如图10所示。Cu(4,4'-dipyridylsulfone) 2SiF 6对C 2H 2的吸附容量比C 2H 4大，特别是在低压区。在298K下，分别在0.01bar和1bar下测得C 2H 2的吸附量为2.65mmol/g和5.27mmol/g。在相同条件下，测得C 2H 4的吸附量仅为0.14mmol/g和1.99mmol/g。 The adsorption isotherm of ethylene and acetylene for Cu(4,4'-dipyridylsulfone) 2 SiF 6 at 298K is shown in Figure 10. The adsorption capacity of Cu(4,4'-dipyridylsulfone) 2 SiF 6 for C 2 H 2 is larger than that of C 2 H 4 , especially in the low pressure area. At 298K, the adsorption capacity of C 2 H 2 was 2.65 mmol/g and 5.27 mmol/g measured at 0.01 bar and 1 bar, respectively. Under the same conditions, the measured adsorption capacity of C 2 H 4 is only 0.14 mmol/g and 1.99 mmol/g.
3、粉末X射线衍射(PXRD)3. Powder X-ray diffraction (PXRD)
图11示出Cu(4,4'-dipyridylsulfone) 2SiF 6的PXRD图谱。 Figure 11 shows the PXRD pattern of Cu(4,4'-dipyridylsulfone) 2 SiF 6.
实施例9Example 9
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例8所得Cu(4,4'-dipyridylsulfone) 2SiF 6装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比1:99)混合气以1.25mL/min 通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC 2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体，当乙炔穿透时，停止吸附，再生后吸附柱可循环使用。 The Cu(4,4'-dipyridylsulfone) 2 SiF 6 obtained in Example 8 was loaded into a 5 cm long adsorption column (inner diameter of 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65° C. for 24 hours. Then, 1 bar of acetylene: ethylene (volume ratio 1:99) mixed gas was passed into the adsorption column at 1.25 mL/min at 25°C, and gas chromatography (GC 2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor Exhaust gas at the outlet of the pipe string. High-purity ethylene (greater than 99.9999%) gas can be obtained from the outflow gas. When the acetylene penetrates, the adsorption is stopped, and the adsorption column can be recycled after regeneration.
实施例10Example 10
采用室温搅拌法合成方法，将0.5mmol Ni(NO 3) 2和0.5mmol(NH 4) 2TiF 6溶于去离子水，1mmol 4,4’-二吡啶砜溶解于无水甲醇中，两者混合，25℃反应24h后得到晶体，所得晶体过滤、甲醇洗涤、干燥，得到Ni(4,4'-dipyridylsulfone) 2TiF 6。 Using room temperature stirring synthesis method, 0.5mmol Ni(NO 3 ) 2 and 0.5mmol(NH 4 ) 2 TiF 6 were dissolved in deionized water, and 1mmol 4,4'-dipyridylsulfone was dissolved in anhydrous methanol. After mixing and reacting at 25°C for 24 hours, crystals are obtained. The crystals obtained are filtered, washed with methanol, and dried to obtain Ni(4,4'-dipyridylsulfone) 2 TiF 6 .
Ni(4,4'-dipyridylsulfone) 2TiF 6的纯气体吸附研究 Study on pure gas adsorption of Ni(4,4'-dipyridylsulfone) 2 TiF 6
Ni(4,4'-dipyridylsulfone) 2TiF 6材料298K时对乙炔的吸附等温线如图12所示。在298K下，分别在0.01bar和1bar下测得C 2H 2的吸附量为1.59mmol/g和3.85mmol/g。 The adsorption isotherm of Ni(4,4'-dipyridylsulfone) 2 TiF 6 at 298K for acetylene is shown in Figure 12. At 298K, the adsorption capacity of C 2 H 2 measured at 0.01 bar and 1 bar is 1.59 mmol/g and 3.85 mmol/g, respectively.
实施例11Example 11
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例10所得Ni(4,4'-dipyridylsulfone) 2TiF 6材料装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比10:90)混合气以1mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体，再生后吸附柱可循环使用。 The Ni(4,4'-dipyridylsulfone) 2 TiF 6 material obtained in Example 10 was loaded into a 5cm long adsorption column (inner diameter 4.6mm), and the sample was first purged with He flow (15mL/min) at 65°C for 24 hours . Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor from the column Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
实施例12Example 12
采用溶剂热法合成方法，将0.5mmol NiNbOF 5溶于DMF溶液，1mmol4,4’-二吡啶砜溶解于无水甲醇中，两者混合，65℃反应24h后得到晶体，所得晶体过滤、甲醇洗涤、干燥，得到Ni(4,4'-dipyridylsulfone) 2NbOF 5。 Using solvothermal synthesis method, 0.5mmol NiNbOF 5 was dissolved in DMF solution, 1mmol 4,4'-dipyridine sulfone was dissolved in anhydrous methanol, the two were mixed, reacted at 65℃ for 24h to obtain crystals, and the crystals obtained were filtered and washed with methanol. And dry to obtain Ni(4,4'-dipyridylsulfone) 2 NbOF 5 .
Ni(4,4'-dipyridylsulfone) 2NbOF 5的纯气体吸附研究 Study on pure gas adsorption of Ni(4,4'-dipyridylsulfone) 2 NbOF 5
Ni(4,4'-dipyridylsulfone) 2NbOF 5材料298K时对乙炔的吸附等温线如图13所示。在298K下，分别在0.01bar和1bar下测得C 2H 2的吸附量为 1.43mmol/g和3.67mmol/g。 The adsorption isotherm of Ni(4,4'-dipyridylsulfone) 2 NbOF 5 at 298K for acetylene is shown in Figure 13. At 298K, the adsorption capacity of C 2 H 2 measured at 0.01 bar and 1 bar is 1.43 mmol/g and 3.67 mmol/g, respectively.
实施例13Example 13
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例12所得Ni(4,4'-dipyridylsulfone) 2NbOF 5材料装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比10:90)混合气以1mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体，再生后吸附柱可循环使用。 The Ni(4,4'-dipyridylsulfone) 2 NbOF 5 material obtained in Example 12 was loaded into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C for 24 hours . Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the column. Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
实施例14Example 14
采用溶剂热法合成方法，将0.5mmol ZnNbOF 5溶于DMF溶液，1mmol4,4’-二吡啶砜溶解于无水甲醇中，两者混合，65℃反应24h后得到晶体，所得晶体过滤、甲醇洗涤、干燥，得到Zn(4,4'-dipyridylsulfone) 2NbOF 5。 Using solvothermal synthesis method, 0.5mmol ZnNbOF 5 was dissolved in DMF solution, 1mmol 4,4'-dipyridine sulfone was dissolved in anhydrous methanol, the two were mixed, reacted at 65℃ for 24h to obtain crystals, the crystals obtained were filtered and washed with methanol And dry to obtain Zn(4,4'-dipyridylsulfone) 2 NbOF 5 .
实施例15Example 15
采用界面慢扩散方法，将溶有0.2mmol 4,4’-二吡啶亚砜的甲醇溶液缓慢滴加在溶有0.1mmol CuMoO 2F 4的乙二醇溶液上，25℃反应72h后过滤、甲醇洗涤、干燥，得到Cu(4,4'-dipyridylsulfoxide) 2MoO 2F 4材料。 Using the slow interface diffusion method, the methanol solution with 0.2mmol 4,4'-dipyridine sulfoxide was slowly dripped onto the ethylene glycol solution with 0.1mmol CuMoO 2 F 4 , reacted at 25°C for 72 hours, then filtered, methanol Washing and drying to obtain Cu(4,4'-dipyridylsulfoxide) 2 MoO 2 F 4 material.
粉末X射线衍射(PXRD)。Powder X-ray diffraction (PXRD).
图14示出Cu(4,4'-dipyridylsulfoxide) 2MoO 2F 4的PXRD图谱。 Figure 14 shows the PXRD pattern of Cu(4,4'-dipyridylsulfoxide) 2 MoO 2 F 4.
实施例16Example 16
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例15所得Cu(4,4'-dipyridylsulfoxide) 2MoO 2F 4材料装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比10:90)混合气以1mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体，再生后吸附柱可循环使用。 Put the Cu(4,4'-dipyridylsulfoxide) 2 MoO 2 F 4 material obtained in Example 15 into a 5 cm long adsorption column (inner diameter of 4.6 mm), and first purge the sample with He flow (15 mL/min) at 65°C 24 hours. Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the column. Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
实施例17Example 17
采用界面慢扩散方法，将溶有0.2mmol 4,4’-二吡啶亚砜的甲醇溶液缓慢滴加在溶有0.1mmol CuNbOF 5的乙二醇溶液上，25℃反应72h后过滤、甲醇洗涤、干燥，得到Cu(4,4'-dipyridylsulfoxide) 2NbOF 5材料。 Using the slow interface diffusion method, the methanol solution with 0.2mmol 4,4'-dipyridine sulfoxide was slowly dropped onto the ethylene glycol solution with 0.1mmol CuNbOF 5 , reacted at 25°C for 72h, filtered, washed with methanol, Dry to obtain Cu(4,4'-dipyridylsulfoxide) 2 NbOF 5 material.
粉末X射线衍射(PXRD)。Powder X-ray diffraction (PXRD).
图15示出Cu(4,4'-dipyridylsulfoxide) 2NbOF 5的PXRD图谱。 Figure 15 shows the PXRD pattern of Cu(4,4'-dipyridylsulfoxide) 2 NbOF 5.
实施例18Example 18
对气体混合物进行穿透测试Penetration testing of gas mixtures
将实施例17所得Cu(4,4'-dipyridylsulfoxide) 2NbOF 5材料装入5cm长的吸附柱(内径4.6mm)中，首先在65℃下用He流(15mL/min)吹扫样品24小时。然后25℃下将1bar的乙炔:乙烯(体积比10:90)混合气以1mL/min通入吸附柱，使用具有火焰离子化检测器(FID)的气相色谱(GC2010Pro,SHIMADZU)监测来自管柱出口的尾气。流出气体中可获得高纯度乙烯(大于99.9999％)气体，再生后吸附柱可循环使用。 The Cu(4,4'-dipyridylsulfoxide) 2 NbOF 5 material obtained in Example 17 was loaded into a 5 cm long adsorption column (inner diameter 4.6 mm), and the sample was first purged with He flow (15 mL/min) at 65°C for 24 hours . Then, 1 bar of acetylene: ethylene (volume ratio 10:90) mixed gas was passed into the adsorption column at 1 mL/min at 25°C, and gas chromatography (GC2010Pro, SHIMADZU) with flame ionization detector (FID) was used to monitor the gas from the column. Outlet exhaust. High-purity ethylene (greater than 99.9999%) gas can be obtained from the effluent gas, and the adsorption column can be recycled after regeneration.
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。In addition, it should be understood that after reading the above description of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims (10)

  1. 一种用于吸附分离乙炔乙烯的层状含氟金属-有机框架材料，其特征在于，结构通式为ML 2A，其中M为金属离子，L为折线型有机配体，A为无机含氟阴离子，金属离子M与折线型有机配体L和无机含氟阴离子A通过配位键桥联形成具有一维孔道的二维网络，相邻二维网络通过超分子作用堆积形成具有永久三维贯穿孔道的层状三维结构； A layered fluorine-containing metal-organic framework material for the adsorption and separation of acetylene ethylene, characterized in that the general structural formula is ML 2 A, where M is a metal ion, L is a polyline-type organic ligand, and A is an inorganic fluorine-containing Anions, metal ions M, broken-line organic ligands L and inorganic fluorine-containing anions A are bridged by coordination bonds to form a two-dimensional network with one-dimensional pores, and adjacent two-dimensional networks are stacked by supramolecular interaction to form permanent three-dimensional through-holes. The layered three-dimensional structure;
    所述金属离子M为Cu 2+、Fe 2+、Co 2+、Ni 2+、Zn 2+中的至少一种； The metal ion M is at least one of Cu 2+ , Fe 2+ , Co 2+ , Ni 2+ , and Zn 2+;
    所述折线型有机配体L为4,4’-二吡啶亚砜、4,4’-二吡啶砜中的至少一种，结构式分别如下式(I)、(II)所示：The polyline-type organic ligand L is at least one of 4,4'-dipyridine sulfoxide and 4,4'-dipyridine sulfone, and the structural formulas are respectively shown in the following formulas (I) and (II):
    Figure PCTCN2021075162-appb-100001
    Figure PCTCN2021075162-appb-100001
    所述无机含氟阴离子A为SiF 6 2-、GeF 6 2-、ZrF 6 2-、SnF 6 2-、TiF 6 2-、NbOF 5 2-、WO 2F 4 2-、MoO 2F 4 2-中的至少一种。 The inorganic fluorine-containing anion A is SiF 6 2- , GeF 6 2- , ZrF 6 2- , SnF 6 2- , TiF 6 2- , NbOF 5 2- , WO 2 F 4 2- , MoO 2 F 4 2 -At least one of.
  2. 根据权利要求1所述的层状含氟金属-有机框架材料，其特征在于，所述金属离子M为Cu 2+、Ni 2+中的至少一种； The layered fluorine-containing metal-organic framework material according to claim 1, wherein the metal ion M is at least one of Cu 2+ and Ni 2+;
    所述折线型有机配体L为4,4’-二吡啶砜；The polyline-type organic ligand L is 4,4'-dipyridylsulfone;
    所述无机含氟阴离子A为SiF 6 2-、GeF 6 2-、TiF 6 2-、NbOF 5 2-中的至少一种。 The inorganic fluorine-containing anion A is at least one of SiF 6 2- , GeF 6 2- , TiF 6 2- , and NbOF 5 2-.
  3. 根据权利要求1或2所述的层状含氟金属-有机框架材料的制备方法，其特征在于，包括步骤：The method for preparing a layered fluorine-containing metal-organic framework material according to claim 1 or 2, characterized in that it comprises the steps of:
    (1)将金属离子无机盐、无机含氟阴离子化合物按配比溶于有机溶剂、去离子水或去离子水和有机溶剂的混合液中，得金属离子-无机含氟 阴离子溶液；将有机配体按配比溶于有机溶剂或去离子水和有机溶剂的混合液中，得有机配体溶液；(1) The metal ion inorganic salt and inorganic fluorine-containing anion compound are dissolved in an organic solvent, deionized water or a mixture of deionized water and organic solvent according to the proportion to obtain a metal ion-inorganic fluorine-containing anion solution; the organic ligand Dissolve in an organic solvent or a mixture of deionized water and an organic solvent according to the ratio to obtain an organic ligand solution;
    (2)将有机配体溶液滴加在金属离子-无机含氟阴离子溶液上方，利用界面扩散法制备得金属-阴离子-有机框架材料；或者直接将有机配体溶液和金属离子-无机含氟阴离子溶液混合，利用溶剂热法制备得金属-阴离子-有机框架材料；或者将有机配体溶液和金属离子-无机含氟阴离子溶液直接混合室温搅拌制备得金属-阴离子-有机框架材料；(2) Drop the organic ligand solution on top of the metal ion-inorganic fluorine-containing anion solution, and use the interface diffusion method to prepare the metal-anion-organic framework material; or directly combine the organic ligand solution and the metal ion-inorganic fluorine-containing anion solution Solution mixing, the metal-anion-organic framework material is prepared by solvothermal method; or the organic ligand solution and the metal ion-inorganic fluorine-containing anion solution are directly mixed and stirred at room temperature to prepare the metal-anion-organic framework material;
    (3)所得金属-阴离子-有机框架材料经过滤、洗涤、干燥得所述层状含氟金属-有机框架材料。(3) The obtained metal-anion-organic framework material is filtered, washed, and dried to obtain the layered fluorine-containing metal-organic framework material.
  4. 根据权利要求3所述的制备方法，其特征在于，所述金属离子无机盐为金属离子M的硝酸盐、氯化盐、乙酸盐、碳酸盐、硫酸盐、高氯酸盐、四氟硼酸盐中的至少一种；The preparation method according to claim 3, wherein the inorganic salt of metal ion is nitrate, chloride, acetate, carbonate, sulfate, perchlorate, tetrafluoroethylene of metal ion M At least one of borates;
    所述有机溶剂为甲醇、乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、乙腈、丙酮、氯仿、二氯甲烷、二甲亚砜、乙二醇、丙三醇中的至少一种。The organic solvent is methanol, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, acetone, chloroform, dichloromethane, dimethylsulfoxide, At least one of ethylene glycol and glycerol.
  5. 根据权利要求3所述的制备方法，其特征在于，所述金属离子无机盐、无机含氟阴离子化合物、有机配体的摩尔比为1:0.5～3:0.5～5。The preparation method according to claim 3, wherein the molar ratio of the metal ion inorganic salt, the inorganic fluorine-containing anion compound, and the organic ligand is 1:0.5-3:0.5-5.
  6. 根据权利要求3所述的制备方法，其特征在于，所述界面扩散法和溶剂热法的反应温度均为10～120℃，反应时间均为1～72h。The preparation method according to claim 3, wherein the reaction temperature of the interfacial diffusion method and the solvothermal method are both 10-120°C, and the reaction time is both 1-72h.
  7. 根据权利要求3所述的制备方法，其特征在于，所述洗涤过程为甲醇洗涤抽滤后，浸泡于甲醇中24～72h；The preparation method according to claim 3, wherein the washing process is methanol washing and suction filtration, followed by soaking in methanol for 24 to 72 hours;
    所述干燥过程为：利用真空脱附、流动气体吹扫，温度为25～120℃，时间为6～72h。The drying process is: using vacuum desorption and purging with flowing gas, the temperature is 25-120°C, and the time is 6-72h.
  8. 根据权利要求1或2所述的层状含氟金属-有机框架材料在吸附分离乙炔乙烯中的应用，其特征在于，以权利要求1或2所述的层状含氟金属-有机框架材料为吸附剂，与含乙炔和乙烯的气体混合物接触进行吸附分离。The application of the layered fluorine-containing metal-organic framework material according to claim 1 or 2 in the adsorption and separation of acetylene ethylene, characterized in that the layered fluorine-containing metal-organic framework material according to claim 1 or 2 is used as The adsorbent is in contact with the gas mixture containing acetylene and ethylene for adsorption separation.
  9. 根据权利要求8所述的应用，其特征在于，所述气体混合物中乙炔与乙烯的体积比为0.05:99.95至10:90；The application according to claim 8, wherein the volume ratio of acetylene to ethylene in the gas mixture is 0.05:99.95 to 10:90;
    所述吸附分离的温度为-5～60℃，所述气体混合物的压力为0.5～5bar。The temperature of the adsorption separation is -5-60°C, and the pressure of the gas mixture is 0.5-5 bar.
  10. 根据权利要求8或9所述的应用，其特征在于，所述吸附分离的温 度为20～60℃，所述气体混合物的压力为0.5～2bar；The application according to claim 8 or 9, characterized in that the temperature of the adsorption separation is 20-60°C, and the pressure of the gas mixture is 0.5-2 bar;
    所述层状含氟金属-有机框架材料选择性吸附乙炔后，脱附即得乙炔；After the layered fluorine-containing metal-organic framework material selectively adsorbs acetylene, acetylene is obtained by desorption;
    所述脱附条件为：真空或惰性气体气氛，脱附温度25～120℃。The desorption conditions are: vacuum or inert gas atmosphere, and the desorption temperature is 25-120°C.
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CN114367270A (en) * 2021-11-30 2022-04-19 浙江大学 Method for separating acetylene and carbon dioxide
CN114854035A (en) * 2022-06-02 2022-08-05 福建师范大学 Carbazolyl hydrogen bond organic framework material and preparation method and application thereof
CN115490874A (en) * 2022-09-21 2022-12-20 中国矿业大学 MOF compound with acetylene and ethylene adsorption separation function and preparation method thereof
CN115490874B (en) * 2022-09-21 2023-08-04 中国矿业大学 MOF compound with acetylene and ethylene adsorption separation function and preparation method thereof
CN115353638A (en) * 2022-09-22 2022-11-18 郑州大学 MOF structure adsorption carrier material, preparation method thereof and application of MOF structure adsorption carrier material in anions in foam extraction solution system
CN115353638B (en) * 2022-09-22 2023-09-19 郑州大学 MOF structure adsorption carrier material, preparation method thereof and application thereof in anions in foam extraction solution system
CN116589695A (en) * 2023-05-17 2023-08-15 浙江师范大学 Ionic metal organic framework material with znv topological structure and preparation and application thereof

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