Polyimide/surface-modified metal organic framework mixed matrix membrane as well as preparation method and application thereof

A technology of metal-organic framework and mixed matrix membrane, which is applied in the direction of separation methods, non-metallic elements, chemical instruments and methods, etc., can solve problems such as the compatibility of mixed matrix membranes, improve interfacial compatibility, and solve interfacial phase problems. Capacitive, simple and controllable effect of the preparation process

Active Publication Date: 2020-05-08
XI AN JIAOTONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] The purpose of the present invention is to provide a polyimide / surface modified metal-organic framework mixed matrix membrane and its preparation method and application, to solve the compatibility problem of the existing mixed matrix membrane

Method used

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  • Polyimide/surface-modified metal organic framework mixed matrix membrane as well as preparation method and application thereof
  • Polyimide/surface-modified metal organic framework mixed matrix membrane as well as preparation method and application thereof
  • Polyimide/surface-modified metal organic framework mixed matrix membrane as well as preparation method and application thereof

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preparation example Construction

[0037] The preparation method of a polyimide / surface-modified metal organic framework mixed matrix film according to an embodiment of the present invention includes the following steps:

[0038] (1) In order to make the interface compatibility between the MOF and the polymer matrix better, dopamine is used to modify the surface of the MOF.

[0039] It specifically includes: adding MOF nanoparticles to a buffer with a pH value of 7.5 to 9.0, the concentration of MOF in the buffer is 0.4 to 0.6 mg / mL, ultrasound for 30 to 90 minutes, and magnetic stirring for 12 to 36 hours to make the dispersion evenly Suspension; then add dopamine to the above suspension, ultrasonic for 15~45min, magnetic stirring for 3~18h; centrifugation, washing with deionized water to neutrality, vacuum drying at 40~80℃ for 24h.

[0040] (2) Add the surface modified MOF to the organic solvent X, ultrasonic and magnetic stirring to make the dispersion uniform; add the polyimide film material, continue ultrasonic a...

Embodiment 1

[0051] The polyimide / surface-modified MOF mixed matrix film prepared in the embodiment of the present invention uses self-made polyimide as the polymer matrix, and the surface-modified AlFu MOF is added to the polymer matrix, wherein, The mass ratio of polyimide to AlFu MOF is 1:0.020. The preparation process of the mixed matrix film is as follows:

[0052] (1) Preparation of polyimide polymer matrix:

[0053] Under the protection of nitrogen, 0.64mmol of homemade diaminodibenzo-18-crown-6 and 1.92mmol of commercial 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane are used as aromatic Diamine monomer is added to 9.2mL N,N-dimethylacetamide, and the diamine solution is obtained after magnetic stirring is completely dissolved; according to the molar ratio of aromatic diamine to aromatic dianhydride of 1:1, 2.56mmol of 4,4'-hexafluoroisopropyl phthalic anhydride solid was directly added to the diamine solution, and stirred at room temperature for 24 hours for solution polycondensat...

Embodiment 2

[0062] Preparation of polyimide / surface modified MOF mixed matrix film. The mixed matrix film uses self-made polyimide as a polymer matrix, and surface-modified AlFu MOF is added to the polymer matrix, wherein the mass ratio of polyimide to AlFu MOF is 1:0.053.

[0063] image 3 It is a scanning electron micrograph of a cross-section of a mixed matrix film made with surface-modified AlFu MOF.

[0064] Under the conditions of 35℃ and 2.0MPa, the polyimide / surface modified MOF mixed matrix film is used for CO 2 / N 2 The separation of mixed gas (20 / 80vol%), its CO 2 Permeability coefficient is 171barrer, CO 2 / N 2 The selectivity is 81; at the same time the mixed matrix membrane is used for CO 2 / CH 4 The separation of mixed gas (10 / 90vol%), its CO 2 Permeability coefficient is 162barrer, CO 2 / N 2 The selectivity is 80.

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Abstract

The invention discloses a polyimide / surface-modified metal organic framework mixed matrix membrane as well as a preparation method and application thereof. The preparation method comprises the following steps: dopamine surface modification is adopted, so that MOF particle agglomeration can be effectively prevented, and the particle size is reduced; meanwhile, the compatibility between an MOF material and a polyimide polymer matrix is improved, and non-selective gaps appearing on a polymer / MOF phase interface are reduced; CO2 / N2 mixed gas and CO2 / CH4 mixed gas permeability separation performance results of the polyimide / surface-modified MOF mixed matrix membrane show that the CO2 permeability coefficient and CO2 / inert gas selectivity of the membrane material can be simultaneously improved by surface modified MOF doping; and the CO2 / N2 mixed gas and CO2 / CH4 mixed gas permeability separation performances both exceed the Robeson upper limit in 2008, the CO2 separation performance of the membrane can be effectively enhanced by preparing the polyimide / surface modified MOF mixed matrix membrane, and the membrane can be applied to the fields of capture of CO2 in flue gas and purification of natural gas.

Description

Technical field [0001] The invention belongs to the technical field of gas membrane separation, and specifically relates to a polyimide / surface-modified metal organic framework mixed matrix membrane and a preparation method and application thereof. Background technique [0002] CO 2 The separation and capture of carbon dioxide has broad application prospects in carbon emission reduction and natural gas purification, and is of great significance for solving energy and environmental problems that restrict human survival and sustainable development. Compared with traditional separation technologies such as rectification and absorption, gas membrane separation technology has attracted wide attention due to its high efficiency, energy saving, and environmental friendliness. [0003] At present, insufficient permeation selectivity of membrane materials is still one of the important factors limiting the large-scale industrial application of gas membrane separation, and the development of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01D67/00B01D71/64B01D53/22C01B32/50C10L3/10
CPCB01D67/0002B01D71/64B01D53/228C10L3/104C01B32/50C10L2290/548Y02C20/40Y02P20/151
Inventor 伊春海吴东云
Owner XI AN JIAOTONG UNIV
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