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Polyimide gas separation membrane as well as preparation method and applications thereof

A technology of gas separation membrane and polyimide, applied in separation methods, semi-permeable membrane separation, dispersed particle separation, etc., can solve the problems of gas selectivity decline, achieve improved gas permeability, high permeability, and suppress tightness stacked effect

Active Publication Date: 2015-08-12
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In order to further improve the gas permeability of the polyimide separation membrane, Calle et al. adopted a bulky structure of 3,3,3", 4"-(5'-tert-butyl-m-trimethylbenzene)tetracarboxylic dianhydride and 2 , 4,6-trimethyl-m-phenylenediamine prepared polyimide separation membrane, the separation membrane showed excellent gas permeability, CO 2 The permeability coefficient is as high as 465barrer, but at the same time the gas selectivity drops significantly, and the CO 2 / CH 4 The selection coefficient is as low as 11.7 (Calle M, Garcia C, Lozano AE, de la Campa JG, de Abajo J, Alvarez C, Local chain mobility dependence on molecular structure in polyimides with bulky side groups: Correlation with gas separation properties, J Membr Sci, 2013, 434, 121-129)

Method used

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  • Polyimide gas separation membrane as well as preparation method and applications thereof
  • Polyimide gas separation membrane as well as preparation method and applications thereof
  • Polyimide gas separation membrane as well as preparation method and applications thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0044] Embodiment 1, the preparation of polyimide gas separation membrane

[0045] In a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet, and a thermometer, add 39.85 grams (0.1 mol) of α,α-bis(4-amino-3,5-dimethylphenyl)-1-( 4'-trifluoromethylphenyl) methane and N-methylpyrrolidone (NMP) 126 grams, stirred under nitrogen protection until completely dissolved, then added 44.42 grams (0.1 mole) 4,4'-(hexafluoroisopropyl Base) two phthalic anhydride (6FDA), to obtain a solid content of 40wt.% of the homogeneous solution. 0.65 g (0.005 mole) of isoquinoline and 21 g of toluene were added to the above homogeneous solution, the temperature of the reaction system was raised to 180° C. and reacted for 12 hours, the toluene was distilled off, and the heating was stopped. Cool the reaction solution to 80-120°C and pour it into methanol to obtain a fibrous crude product, collect the precipitated crude product, wash repeatedly with me...

Embodiment 2

[0049] Embodiment 2, the preparation of polyimide gas separation membrane

[0050] In a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet, and a thermometer, add 34.85 grams (0.1 moles) of α,α-bis(4-amino-3,5-dimethylphenyl)-1-( 4'-fluorophenyl)methane and N,N-dimethylacetamide (DMAc) 147 grams, stirred under nitrogen protection until completely dissolved, then added 44.42 grams (0.1 mole) 4,4'-(hexafluoroiso Propyl) diphthalic anhydride (6FDA) to obtain a homogeneous solution with a solid content of 35wt.%. 1.29 grams (0.01 moles) of quinoline and 25 grams of xylene were added to the above homogeneous solution, the temperature of the reaction system was raised to 140° C. for 12 hours, the xylene was distilled off, and the heating was stopped. Cool the reaction solution to 80-120°C and pour it into ethanol to obtain a fibrous crude product, collect the precipitated crude product, wash repeatedly with ethanol and water, filte...

Embodiment 3

[0052] Embodiment 3, the preparation of polyimide gas separation membrane

[0053] In a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet, and a thermometer, add 38.44 grams (0.1 mol) of α,α-bis(4-amino-3,5-dimethylphenyl)-1-( 3',4',5'-trifluorophenyl) methane and N-methylpyrrolidone (NMP) 154 grams, stirred under nitrogen protection until completely dissolved, then added 44.42 grams (0.1 mol) 4,4'-( Hexafluoroisopropyl) diphthalic anhydride (6FDA) to obtain a homogeneous solution with a solid content of 35wt.%. 1.29 grams (0.01 moles) of quinoline and 26 grams of toluene were added to the above-mentioned homogeneous solution, the temperature of the reaction system was raised to 180° C. and reacted for 10 hours, the toluene was distilled off, and the heating was stopped. Cool the reaction solution to 80-120°C and pour it into ethanol to obtain a fibrous crude product, collect the precipitated crude product, wash repeatedly w...

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Abstract

The invention discloses a polyimide gas separation membrane as well as a preparation method and applications thereof. The separation membrane is made of a polyimide resin which is shown in a formula I and has a fluorobenzene side group containing structure. The polyimide gas separation membrane has the characteristics of high permeability and high selectivity, the permeability coefficient to CO2 is greater than or equal to 180 barrer, the selective coefficient to CO2 / CH4 is greater than 30, and the separation membrane shows excellent heat resistance and mechanical properties. The gas separation membrane has an important application value in various CO2-related separation and recovery applications such as the separation of carbon dioxide and methane in biological gas, the removal of acid gases such as carbon dioxide and the like, the recovery of carbon dioxide in tertiary oil recovery of oil fields, and the like.

Description

technical field [0001] The invention relates to the field of membrane technology, in particular to a high-permeability and high-selectivity polyimide gas separation membrane and its preparation method and application. Background technique [0002] The use of membrane separation method to separate gas has been more and more widely used in industrial gas separation and purification in recent years due to its advantages of high separation efficiency, low energy loss, green environmental protection, simple operation, safety and reliability, and easy installation and debugging. . Membrane materials are the core of gas separation membrane technology. The current commercialized gas separation membrane materials are mainly cellulose (CA), polysulfone (PSF), polydimethylsiloxane (PDMS), polyphenylene oxide (PPO), etc. polymer film. However, the heat resistance of these gas separation membranes is not ideal, and the glass transition temperature does not exceed 200°C, so they are lim...

Claims

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Application Information

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IPC IPC(8): C08J5/18C08G73/10B01D53/22B01D71/64
CPCY02C20/40Y02P20/151
Inventor 范琳佟辉杨士勇
Owner INST OF CHEM CHINESE ACAD OF SCI
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