CN110465272A - A kind of two-dimensional metallic-organic framework material is in SF6/N2Application in separation - Google Patents

A kind of two-dimensional metallic-organic framework material is in SF6/N2Application in separation Download PDF

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Publication number
CN110465272A
CN110465272A CN201910849158.9A CN201910849158A CN110465272A CN 110465272 A CN110465272 A CN 110465272A CN 201910849158 A CN201910849158 A CN 201910849158A CN 110465272 A CN110465272 A CN 110465272A
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separation
mof
ome
organic framework
dimensional metallic
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阳庆元
刘磊
常苗
刘大欢
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—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]

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A kind of two-dimensional metallic-organic framework material (Cu-MOF-OMe) is in SF6/N2Application in separation, belongs to new material technology field.The material ligand of class containing C-H and unsatuated metal site for sulfur hexafluoride, can be with formed stronger affinity (multiple spot model ylid bloom action).But it is relatively small to the active force of nitrogen, thus to SF6/N2It is effectively separated.The result shows that under 1.0 bar, Cu-MOF-OMe material is to SF in 298 K6/N2Separation selectivity is 361, the comprehensive separating property index of adsorptive selectivity parameter SSP() it is 780, considerably beyond all porous materials reported in document, and material also has good hydrothermal stability and reproducibility, is SF6/N2Separation, which provides, efficiently separates material, in SF6Being enriched with use aspects has important industrial value.

Description

A kind of two-dimensional metallic-organic framework material is in SF6/N2Application in separation
Technical field
The present invention relates to a kind of two-dimensional metallic-organic framework materials (metal-organic frameworks, MOFs) New application, using the material to SF6/N2It is separated, belongs to new material technology field.
Background technique
Due to SF6With excellent dielectric and arc extinction performance and hypotoxicity and high stability, be power Transmission equipment and Extensive insulation and switching medium are used in semicon industry.SF6A kind of greenhouse gases as high intensity exist in an atmosphere Service life it is very long, about 3200.And isometric SF6Caused greenhouse effects are CO223900 times, it is by " capital of a country Protocol " it is classified as one of the six kinds of greenhouse gases for forbidding discharge.The SF in industrial application6And N2It is usually used in mixed way, works as SF6With N2When mixing, even if in high N2Under concentration, fluid mixture is also able to maintain pure SF6High dielectric strength.But when mix this two SF when kind gas6The complexity of recycling increases, as SF in mixture6Amount reduce when, situation becomes apparent.Therefore, there is an urgent need to Exploitation efficiently separates SF6/N2The method of mixture is to prevent SF6It discharges into the atmosphere.In general, SF6/N2Mixture has passed through liquid Change separation, this is energy-intensive, especially for diluted SF6Concentration.Therefore, such as pressure-variable adsorption (pressure Swing adsorption, PSA) energy saving adsorption separation process be considered as a kind of alternative scheme.Pressure-variable adsorption, which has, to be thrown Provide the advantages that at low cost, easy to operate, energy saving.
Metal-organic framework materials are a kind of novel porous materials, have specific pore structure and big surface area and Porosity.The most significant characteristic of MOFs is their adjustable apertures and the function by various organic linkers and metallic combination Energy.Due to these characteristics, MOFs is considered as the potential material of many applications, for example, gas storage, gas separate, drug is defeated It send, be catalyzed and sense.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation method of metal-organic framework materials and being applied to Sulfur hexafluoride and nitrogen separation.
The technical scheme is that
A kind of preparation method of metal-organic framework materials, includes the following steps:
Firstly, by Cu (NO3)2.3H2O, 5- methoxyl group M-phthalic acid, pyridine and methanol (200 mL) are placed in a beaker, and It is put into rotor in beaker, then by reaction solution ultrasound certain time, is completely dissolved reactant, stirs 12 at normal temperatures and pressures h.To obtain blue colored crystal powder after reaction, is handled using n,N-Dimethylformamide and methanol solvate and washed repeatedly Sample several times, dissolves the unreacted ligand in material, and change fresh solvent and be repeated several times.Then by sample It filters and is placed in save in centrifuge tube after vacuum and heating drying and place.
It weighs a certain amount of drying sample and is placed in testing tube and carry out vacuum outgas, test 77 K respectively after to be de-gassed Sulfur hexafluoride and nitrogen adsorption under nitrogen, 273 K and 298 K.
After to be tested, using two point Langmuir (Dual-Sites Langmuir, DSL) model to adsorption isotherm Line carries out regression fit, is then calculated using Ideal adsorption solution theory (IAST) separation selectivity.
Detailed description of the invention
The crystal structure figure of Fig. 1 Cu-MOF-OMe: c-axis direction
The crystal structure figure of Fig. 2 Cu-MOF-OMe: b axis direction
The PXRD spectrogram of Fig. 3 Cu-MOF-OMe
The thermogravimetric curve of Fig. 4 Cu-MOF-OMe
The specific surface area of Fig. 5 Cu-MOF-OMe
The infrared spectrum of Fig. 6 Cu-MOF-OMe
The scanning electron microscope of Fig. 7 Cu-MOF-OMe
SF of Fig. 8 Cu-MOF-OMe at 298 K6And N2Adsorption-desorption isothermal
SF of Fig. 9 Cu-MOF-OMe at 298 K6And N2IAST ideal selectivity
Figure 10 SF6/N2Separating property compares: the SF in 298 K and 1.0 bar6Adsorbance and selectivity relationship
Figure 11 SF6/N2Separating property compares: adsorptive selectivity parameter compares under 298 K
The regeneration tests of Figure 12 Cu-MOF-OMe.
Specific embodiment
In order to obtain preferably separating sulfur hexafluoride and nitrogen mixture and be enriched with sulfur hexafluoride gas, we pass through Consulting literatures recognize that without dipole moment, the quadrupole moment of nitrogen is greater than sulfur hexafluoride, the polarization of sulfur hexafluoride for sulfur hexafluoride and nitrogen Rate is higher than nitrogen, and the ligand of class containing C-H and the metal organic framework material containing unsatuated metal site for sulfur hexafluoride Material can be still relatively small to the active force of nitrogen with formed stronger affinity, therefore in metal-organic framework materials In duct introduce containing C-H organic group abundant and unsatuated metal site come modify duct internal environment can with it is lithium Sulphur forms stronger affinity to achieve the purpose that separate sulfur hexafluoride nitrogen mixture.
Embodiment 1
Firstly, by Cu (NO3)2.3H2O(2.4 g, 10 mmol), 5- methoxyl group M-phthalic acid (2.12 g, 10 mmol), pyrrole Pyridine (0.8 g, 10 mmol) and methanol (200 mL) are placed in a beaker, and rotor is put into beaker, then surpass reaction solution Sound certain time, is completely dissolved reactant, stirs 12 h at normal temperatures and pressures.To obtain blue colored crystal powder after reaction End, using n,N-Dimethylformamide, washing sample several times, dissolves the unreacted ligand in material, and change fresh repeatedly Solvent be repeated several times.The above-mentioned sample handled by n,N-Dimethylformamide is recycled at methanol solvate Reason repeatedly impregnates several times sample, it is therefore an objective to displace the high boiling n,N-Dimethylformamide in material duct, then It is placed being placed in save in centrifuge tube after sample filtering and vacuum and heating drying.
Embodiment 2
It weighs a certain amount of drying sample to be placed in testing tube, and testing tube is mounted on health tower adsorption instrument (Quantachrome Autosorb-IQ), deaerate under 393 K 12 h, in order to remove the solvent in duct.After to be de-gassed Test 77 K nitrogen respectively, sulfur hexafluoride and nitrogen adsorption under 273 K and 298 K.Adsorption experiment data based on one pack system, material The selectivity of material is calculated using Ideal adsorption solution theory (IAST), and wherein the adsorption isotherm of one pack system is blue using two point Ge Miaoer (Dual-Sites Langmuir, DSL) model is returned.
Two-dimensional metallic organic framework material, Cu-MOF-OMe described in this work.The material shows highest at present SF6/N2Separation selectivity (361) and SSP(780) value, wherein SSP is comprehensive separating property index.The result of experiment also indicates that material Expect that the heterogeneity hole in sulfur hexafluoride and skeleton generates stronger effect.Meanwhile the material also has preferable hydrothermally stable Property and regenerability.

Claims (4)

1. a kind of two-dimensional metallic-organic framework material is in SF6/N2Application in separation, the metal-organic framework materials are Cu-MOF-OMe is used for SF6/N2Efficiently separate.
2. purposes described in accordance with the claim 1, which is characterized in that metal-organic framework materials used are Cu-MOF-OMe, Its operating temperature range is between 273 K to 298 K.
3. purposes described in accordance with the claim 1, which is characterized in that its separation method includes Batch Adsorption separation.
4. purposes described in accordance with the claim 1, which is characterized in that separated object includes SF6/N2Mixture.
CN201910849158.9A 2019-09-09 2019-09-09 A kind of two-dimensional metallic-organic framework material is in SF6/N2Application in separation Pending CN110465272A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112724418A (en) * 2021-01-18 2021-04-30 北京化工大学 Preparation method and application of calcium-based metal organic framework material
CN116120568A (en) * 2022-11-23 2023-05-16 大连佳纯气体净化技术开发有限公司 Hollow MOFs (metal-organic frameworks), preparation method thereof and SF (sulfur hexafluoride) thereof 6 /N 2 Application in separation field
CN117205705A (en) * 2023-11-09 2023-12-12 天津工业大学 The aluminum-based metal-organic framework material is shown in C 3 F 8 /N 2 Application in separation

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CN105813711A (en) * 2013-08-05 2016-07-27 纽麦特科技公司 Metal organic frameworks for electronic gas storage
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112724418A (en) * 2021-01-18 2021-04-30 北京化工大学 Preparation method and application of calcium-based metal organic framework material
CN116120568A (en) * 2022-11-23 2023-05-16 大连佳纯气体净化技术开发有限公司 Hollow MOFs (metal-organic frameworks), preparation method thereof and SF (sulfur hexafluoride) thereof 6 /N 2 Application in separation field
CN116120568B (en) * 2022-11-23 2024-05-31 大连佳纯气体净化技术开发有限公司 Hollow MOFs (metal-organic frameworks), preparation method thereof and SF (sulfur hexafluoride) thereof6/N2Application in separation field
CN117205705A (en) * 2023-11-09 2023-12-12 天津工业大学 The aluminum-based metal-organic framework material is shown in C 3 F 8 /N 2 Application in separation
CN117205705B (en) * 2023-11-09 2024-02-02 天津工业大学 The aluminum-based metal-organic framework material is shown in C 3 F 8 /N 2 Application in separation

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Application publication date: 20191119