CN113680332A - For CO2Preparation method of adsorbed C-MOF-5/Pebax composite material - Google Patents

For CO2Preparation method of adsorbed C-MOF-5/Pebax composite material Download PDF

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CN113680332A
CN113680332A CN202111023257.5A CN202111023257A CN113680332A CN 113680332 A CN113680332 A CN 113680332A CN 202111023257 A CN202111023257 A CN 202111023257A CN 113680332 A CN113680332 A CN 113680332A
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mof
carbon dioxide
pebax
solution
hours
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盖方圆
李智博
赵晓刚
刘振国
王严
张铁欣
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Changchun University of Technology
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Changchun University of Technology
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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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention relates to the technical field of adsorption materials, in particular to a preparation method of a C-MOF-5/Pebax composite material for carbon dioxide adsorption, which comprises the following steps: the Pebax-1657 as a polyether block amide material has the advantages of no toxicity, green, environmental protection and the like, and has stronger affinity to carbon dioxide due to specific carbonyl, ether bond and other groups, so that the Pebax-1657 as a polymer carrier provides a new method for producing a renewable and low-cost carbon dioxide adsorbent. The MOF-5 is a nano material with a typical microporous structure, and has high specific surface area and microporous pores, so that the MOF-5 has strong adsorption force on carbon dioxide molecules, and the carbonization treatment on the basis can increase mesopores while keeping the microporous volume, thereby being beneficial to the rapid mass transfer of the carbon dioxide molecules. The invention aims to relieve global warming and provides a new idea for preparing a material for adsorbing carbon dioxide.

Description

For CO2Preparation method of adsorbed C-MOF-5/Pebax composite material
Technical Field
The invention relates to a preparation method of a C-MOF-5/Pebax composite material for carbon dioxide adsorption.
Background
At present, global warming is a problem of general public concern, carbon dioxide is a major factor of global warming, the concentration of fossil fuel in the atmosphere is continuously increasing due to large-scale combustion thereof, and it is capable of absorbing heat radiation. In recent years, many extreme weathers such as heavy rainfall, high temperature heat wave and the like are closely related to the increase of carbon dioxide concentration in the atmosphere and greenhouse gas effect. The greenhouse effect can also cause the sea level to rise, destroy the living environment and the ecosystem of human beings, and even some organisms can be difficult to kill by adapting to the change of the environmental temperature. Therefore, in consideration of the importance of reducing energy consumption and relieving global warming, the synthesis of materials capable of reducing carbon dioxide in the atmosphere and the production of materials which are green, environment-friendly and nontoxic and have excellent adsorption performance have very important significance.
The Pebax-1657 as a polyether block amide material has the advantages of no toxicity, green, environmental protection and the like, and has stronger affinity to carbon dioxide due to specific carbonyl, ether bond and other groups, so that the Pebax-1657 as a polymer carrier provides a new method for producing a renewable and low-cost carbon dioxide adsorbent.
The MOF-5 is a nano material with a typical microporous structure, has high specific surface area and microporous pores, so that the MOF-5 has strong adsorption force on carbon dioxide molecules, and is subjected to carbonization treatment on the basis of the strong adsorption force to increase mesopores while keeping the microporous volume, thereby being beneficial to the rapid mass transfer of the carbon dioxide molecules.
Disclosure of Invention
The invention aims to solve the problems of global warming, equipment corrosion caused by traditional amine solutions and the like.
Another object of the present invention is to provide a method for preparing an adsorbent material, comprising the steps of:
a preparation method of a C-MOF-5/Pebax composite material for carbon dioxide adsorption is characterized by comprising the following steps:
s1: preparing C-MOF-5;
s2: adding a proper amount of Pebax-1657 into a mixed solvent of ethanol and water, wherein the mass ratio of the ethanol to the water is 7:3, and then carrying out condensation reflux at 80 ℃ for 4-6 hours to obtain a polymer solution;
s3: and mixing the prepared polymer solution with a certain amount of C-MOF-5, carrying out ultrasonic treatment to a uniform state, centrifuging to remove supernatant, and drying the obtained product at 60 ℃ for 24 hours to obtain the adsorbing material.
The method for preparing the adsorbing material according to claim 1, wherein the C-MOF-5 is obtained by the following method:
1) 2.11 g of zinc acetate dihydrate (Zn (OAc)2·2H2O) was dissolved in 62.5 ml of N, N-Dimethylformamide (DMF), designated as solution A, and 0.631g of terephthalic acid (H)2BDC) was dissolved in 50 ml DMF and was named solution B. A, B the solutions were sonicated for 30 minutes to achieve uniform dispersion, and solution A was slowly poured into solution B while maintaining agitation for 3 hours. Centrifuging the solution, pouring out supernatant, washing the sample with ethanol, repeating the washing for three times to obtain a sample, and drying for later use;
2) carbonizing in a horizontal tube furnace, feeding the ceramic boat filled with the MOF-5 powder into the tube furnace, heating the sample to 350 ℃ at the heating rate of 5 ℃/min under the nitrogen flow rate of 10mL/min, and keeping the temperature for 1 hour to finally obtain a carbonized material, namely C-MOF-5.
The method according to claim 1, wherein the polymer solution is present in an amount of 5% by mass.
The mixed solvent used for the polymer solution according to claim 3, wherein the mass ratio of the ethanol to the water is controlled to be 7: 3-8: 2.
The preparation method of the adsorbing material according to claim 1, wherein the C-MOF-5 and the polymer solution are subjected to ultrasonic treatment for 1-2 hours.
A process for CO according to claim 12The preparation method of the adsorbed C-MOF-5/Pebax composite material is characterized in that the molecular acting force in the polymer is improved to a certain extent by the C-MOF-5, and the absorption of carbon dioxide is enhanced.
The adsorbent material according to claim 1, wherein the material is used for carbon dioxide adsorption.
The method takes zinc acetate, terephthalic acid and Pebax-1657 as raw materials to prepare the C-MOF-5/Pebax composite material for carbon dioxide adsorption. The success of the combination can be proved by a scanning electron microscope, an infrared spectrum and X-ray diffraction, and the material has higher thermal stability by thermogravimetric spectrum analysis.
The invention improves the absorption effect of polymer intermolecular structure enhancement on carbon dioxide by compounding the hierarchical porous material in the polyether block amide polymer.
The raw materials adopted by the invention are cheap and easy to obtain, the synthesis yield is high, and the adsorbent accords with green chemical conditions and has better adsorption performance. The results show that the C-MOF-5/Pebax material has a good industrial production prospect, so that the C-MOF-5/Pebax composite material can be used for adsorbing carbon dioxide to achieve the purposes of reducing the greenhouse effect, reducing the concentration of carbon dioxide in the atmosphere and relieving the ecological pressure.
Drawings
FIG. 1 is an X-ray diffraction pattern of the C-MOF-5/Pebax composite prepared in example 1;
FIG. 2 is an infrared spectrum of the C-MOF-5/Pebax composite prepared in example 1;
FIG. 3 is an SEM image of the C-MOF-5/Pebax composite prepared in example 1;
FIG. 4 is a TGA profile of the C-MOF-5/Pebax composite prepared in example 1;
FIG. 5 is the CO of the C-MOF-5/Pebax composite prepared in example 12And (5) absorbing the attached drawings.
Detailed Description
The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 1
A preparation method of an adsorbing material specifically comprises the following steps:
dissolving a certain amount of dried Pebax-1657 in a mixed solvent with the mass ratio of ethanol to water being 7:3, and refluxing for 3 hours at 80 ℃ to obtain a polymer solution with the mass fraction of 5%.
2.11 g of zinc acetate dihydrate (Zn (OAc)2·2H2O) was dissolved in 62.5 ml of N, N-Dimethylformamide (DMF), designated as solution A, and 0.631g of terephthalic acid (H)2BDC) was dissolved in 50 ml DMF and was named solution B. A, B the solutions were sonicated for 30 minutes to achieve uniform dispersion, and solution A was slowly poured into solution B while maintaining agitation for 3 hours. Centrifuging the solution, pouring out supernatant, washing the sample with ethanol, repeating the steps for three times to obtain a sample, and drying the sample for later use.
Carbonizing in a horizontal tube furnace, feeding the ceramic boat filled with the MOF-5 powder into the tube furnace, heating the sample to 350 ℃ at the heating rate of 5 ℃/min under the nitrogen flow rate of 10mL/min, and keeping the temperature for 1 hour to finally obtain a carbonized material, namely C-MOF-5.
Dispersing the C-MOF-5 into ethanol, performing ultrasonic treatment for 1-2 hours, dropwise adding the mixture into a polymer solution in a magnetic stirring state, centrifuging the mixture after 6 hours, and drying the obtained material in an oven at 60 ℃ for 12 hours to obtain a polymer film or powder of the composite C-MOF-5.
The PA section in the Pebax-1657 adopted in the embodiment 1 provides good thermal stability for the composite material; the PEO section has stronger affinity to polar molecules and has certain advantage on carbon dioxide adsorption.
The composite material prepared in example 1 is shown in fig. 3, fig. 3(a) shows that the prepared C-MOF-5 has a complete cubic structure, has clear edges and is better in dispersibility, and fig. 3(B) shows that the MOF-compounded polymer material has uniform MOF dispersion on the polymer under clear folds. The material is not seriously agglomerated after being compounded.
The X-ray diffraction pattern of the C-MOF-5/Pebax composite material prepared in example 1 is shown in figure 1, and the diffraction peaks of the two materials can be observed from the X-ray diffraction pattern of the composite material in figure 1, wherein the diffraction peaks of Pebax-1657 appear at 20 degrees and 24.2 degrees, which indicates that the structure and the crystallinity of the MOF are not damaged by the incorporation of the polymer.
The infrared spectrum of the C-MOF-5/Pebax composite material prepared in example 1 is shown in FIG. 2, and is 3200cm-1The characteristic peak of the polymer Pebax-1657 can be observed at 1590cm-1A characteristic peak of C-MOF-5 can be observed, and the infrared spectrum can effectively illustrate the effective combination of the MOF and the polymer.
The thermogravimetric spectrum of the C-MOF-5/Pebax composite material prepared in example 1 is shown in FIG. 4, and the material has little great weight loss before 320 ℃, although the pyrolysis temperature is slightly reduced compared with that of a pure polymer, the thermal spectrum still can meet the industrial requirement.
CO of C-MOF-5/Pebax composite prepared in example 12The absorption spectrum is shown in FIG. 5, which shows that the absorption capacity of the material to carbon dioxide can reach 1.16 mmol/g-1。

Claims (7)

1. For CO2The preparation method of the adsorbed C-MOF-5/Pebax composite material is characterized by comprising the following steps:
s1: preparing C-MOF-5;
s2: adding a proper amount of Pebax-1657 into a mixed solvent of ethanol and water, wherein the mass ratio of the ethanol to the water is 7:3, and then carrying out condensation reflux at 80 ℃ for 4-6 hours to obtain a polymer solution;
s3: and mixing the prepared polymer solution with a certain amount of C-MOF-5, carrying out ultrasonic treatment to a uniform state, centrifuging to remove supernatant, and drying the obtained product at 60 ℃ for 24 hours to obtain the adsorbing material.
2. The method for preparing the adsorbing material according to claim 1, wherein the C-MOF-5 is obtained by the following method:
1) 2.11 g of zinc acetate dihydrate (Zn (OAc)2·2H2O) was dissolved in 62.5 ml of N, N-Dimethylformamide (DMF), designated as solution A, and 0.631g of terephthalic acid (H)2BDC) was dissolved in 50 ml DMF, designated solution B; respectively carrying out ultrasonic treatment on A, B two solutions for 30 minutes to achieve the purpose of uniform dispersion, slowly pouring the solution A into the solution B, keeping the stirring state for 3 hours, centrifuging the solution, pouring out supernatant, washing the sample with ethanol, repeating the steps for three times to obtain a sample, and drying for later use;
2) carbonizing in a horizontal tube furnace, feeding the ceramic boat filled with the MOF-5 powder into the tube furnace, heating the sample to 350 ℃ at the heating rate of 5 ℃/min under the nitrogen flow rate of 10mL/min, and keeping the temperature for 1 hour to finally obtain a carbonized material, namely C-MOF-5.
3. The method according to claim 1, wherein the polymer solution is present in an amount of 3 to 5% by weight.
4. The polymer solution according to claim 3, wherein the mass ratio of the ethanol to the water is controlled to be 7: 3-8: 2.
5. The preparation method of the adsorbing material according to claim 1, wherein the C-MOF-5 and the polymer solution are subjected to ultrasonic treatment for 1-2 hours.
6. The preparation method of the C-MOF-5/Pebax composite material for adsorbing the carbon dioxide, according to claim 1, wherein the C-MOF-5 improves molecular force in the polymer to a certain extent, and is beneficial to enhancing the absorption of the carbon dioxide.
7. The adsorbent material according to claim 1, wherein the material is used for carbon dioxide adsorption.
CN202111023257.5A 2021-09-02 2021-09-02 For CO2Preparation method of adsorbed C-MOF-5/Pebax composite material Pending CN113680332A (en)

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