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Polymer embedded metal organic framework membrane, preparation method, device and application thereof

A metal-organic framework and polymer technology, applied in separation methods, chemical instruments and methods, membrane technology, etc., can solve the problems of poor gas separation effect, low utilization rate of raw materials, low selectivity, etc., to reduce energy, improve Harness the effect of efficiency, simplifying synthesis and modification steps

Active Publication Date: 2015-11-04
ZHEJIANG UNIV OF TECH
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  • Abstract
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  • Claims
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Problems solved by technology

(1) Synthetic method, the currently used synthetic method is mainly solvothermal synthesis, which has the disadvantages of high energy consumption, low raw material utilization rate, and difficulty in scaling up.
(2) Separation effect. The metal organic framework gas separation membrane gas separation effect currently used is poor, because the pore structure of the metal organic framework is not completely continuously increased, such as Cu 2 (BTC) 3 , a metal-organic framework material commonly used in the preparation of gas separation membranes, its pore size is 0.9nm, which is larger than the general small molecule gas, so its gas separation performance depends on the preferential adsorption mechanism, and its H 2 / CO 2 、H 2 / O 2 、H 2 / N 2 、H 2 / CH 4 The gas selectivity is generally less than 20; another example is ZIF-8, a metal organic framework material commonly used in the preparation of gas separation membranes. Although it has a relatively suitable pore structure of 0.34nm, the metal organic framework membrane structure is flexible, resulting in The selectivity is usually not great

Method used

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  • Polymer embedded metal organic framework membrane, preparation method, device and application thereof

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Embodiment 1

[0029] The preparation of embodiment 1 metal organic framework ZIF-8 film

[0030] (1) Cut out a polyvinylidene fluoride hollow fiber membrane with a length of 6 cm, place it in a 30 wt % aqueous solution of ethylenediamine, seal it under the condition of 100 ° C for 12 h, take out the membrane after natural cooling, and use After washing with ion water for three times and drying, it is packaged in a cross-flow membrane module to form a hollow fiber membrane module.

[0031] (2) Preparation of metal-organic framework precursor solution: 2-methylimidazole (0.21g, 2.5mmol) and Zn(NO 3 ) 2 ·6H 2 O (0.37g, 1.25mmol) was dissolved in 1000ml deionized water respectively to obtain 2-methylimidazole solution and Zn(NO 3 ) 2 solution.

[0032] (3) Preparation of membrane: the heater outside the hollow fiber membrane module 5 is preset at 30°C, and the 2-methylimidazole solution obtained in step (2) and Zn(NO 3 ) 2 The solution is respectively placed in the first feed tank 1 and ...

Embodiment 2

[0034] Example 2 Preparation of metal-organic framework ZIF-8 film embedded in polyvinyl alcohol

[0035] (1) Cut a 6cm-long polyvinylidene fluoride hollow fiber membrane, place it in a 30wt% aqueous solution of ethylenediamine, seal it at 100°C for 12h, take out the membrane after natural cooling, and wash it with water After three times of drying, it is packaged in a cross-flow membrane module to form a hollow fiber membrane module.

[0036] (2) Preparation of metal-organic framework precursor solution: 2-methylimidazole (0.21g, 2.5mmol) and Zn(NO 3 ) 2 ·6H 2 O (0.37g, 1.25mmol) was dissolved in 1000ml of deionized water respectively, and 0.5g polyvinyl alcohol was added in the 2-methylimidazole solution to obtain a 2-methylimidazole solution containing polyvinyl alcohol and Zn(NO 3 ) 2 solution.

[0037] (3) Preparation of membrane: the heater outside the hollow fiber membrane module 5 is preset at 60°C, and the 2-methylimidazole solution containing polyvinyl alcohol o...

Embodiment 3

[0039] Example 3 Preparation of metal-organic framework ZIF-8 film embedded with polyethylene glycol

[0040] (1) Cut a 6cm-long polyvinylidene fluoride hollow fiber membrane, place it in a 30wt% aqueous solution of ethylenediamine, seal it at 100°C for 12h, take out the membrane after natural cooling, and wash it with water After three times of drying, it is packaged in a cross-flow membrane module to form a hollow fiber membrane module.

[0041] (2) Preparation of metal-organic framework precursor solution: dissolve 2-methylimidazole (21g, 250mmol) and Zn(NO 3 ) 2 ·6H 2 O (37g, 125mmol) is dissolved in the deionized water of 1000ml respectively, and the polyethylene glycol of 10g is added in the 2-methylimidazole solution, obtains the 2-methylimidazole solution containing polyethylene glycol and Zn(NO 3 ) 2 solution.

[0042] (3) Preparation of membrane: the heater outside the hollow fiber membrane module 5 is preset at 30°C, and the 2-methylimidazole solution containin...

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Abstract

The invention provides a polymer embedded metal organic framework membrane, a preparation method, a preparation device and application thereof. The preparation method includes: (1) encapsulating a hollow fiber membrane in a cross-flow membrane module to form a hollow fiber membrane module; (2) dissolving a metal salt and a ligand in a solvent respectively to obtain a metal salt solution and a ligand solution; (3) respectively pumping the metal salt solution and the ligand solution into a shell pass and a pipe pass of the hollow fiber membrane module at the same time to conduct membrane synthesis, performing pumping at 30-60DEG C continuously for 12-48h, then pumping an alcohol solvent or water into the shell pass and the pipe pass of the hollow fiber membrane module respectively to clean the membrane, and finally drying the membrane, thus obtaining the polymer embedded metal organic framework membrane. The membrane obtained by the invention can be applied to mixed gas separation. According to the invention, a to-be-embedded polar polymer is added directly in synthesis of the metal organic framework membrane, the traditional way of first synthesis and then modification is abandoned, and the method is concise, efficient and low in cost.

Description

(1) Technical field [0001] The invention relates to a metal-organic framework membrane, its preparation method, preparation device and application, in particular to a preparation method, preparation device and application of a polymer-embedded metal-organic framework membrane and its large-scale production, belonging to the preparation of porous membranes and the technical field of gas separation applications. (2) Background technology [0002] In recent years, the combustion of a large amount of fossil fuels has caused a large amount of greenhouse gas emissions such as carbon dioxide, which has brought serious environmental pollution problems. Therefore, in order to reduce greenhouse gas emissions, a new generation of clean energy needs to be developed urgently. Hydrogen is a new energy source with high combustion value, and only produces water after use. It is considered to be the main next-generation clean energy source. Therefore, the separation of hydrogen energy has ...

Claims

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Application Information

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IPC IPC(8): B01D71/82B01D71/34B01D71/64B01D69/08B01D69/10B01D67/00B01D53/22
Inventor 张国亮张从阳李万斌苏鹏程孟琴
Owner ZHEJIANG UNIV OF TECH
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