KR102433978B1 - Polymer separation membrane comprising defect-engineered nanoparticle and method for preparing the same - Google Patents

Abstract

The present invention is a polymer membrane material; and metal-organic framework (MOF) nanoparticles dispersed in the polymer membrane material and having controlled defects. As a result, the composite polymer separation membrane including the nanoparticles with controlled defects of the present invention artificially creates a defect by synthesizing it using an additive in the manufacture of a metal-organic framework (MOF), and the defect manufactured accordingly By complexing the controlled nanoparticles with a polymer membrane, gas permeability is improved while maintaining selectivity, thereby significantly improving separation performance compared to a composite polymer membrane incorporating conventional nanoparticles.

Description

Composite polymer separation membrane comprising defect-controlled nanoparticles and method for manufacturing the same

The present invention relates to a composite polymer membrane and a method for manufacturing the same, and more particularly, to a composite polymer membrane with improved separation performance including nanoparticles with controlled defects and a method for manufacturing the same.

Polymer membranes are attracting attention as a key element in various scientific and technological fields such as electronic materials, pharmaceutical manufacturing, food packaging, protective equipment, fuel cells, water purification, gas, and vapor separation. The separation membrane has the characteristic of controlling the permeation rate of a substance passing through it using a driving force such as concentration, pressure, and potential difference, so it can be applied to the above fields. , MF), ultrafiltration (UF), reverse osmosis (RO), pervaporation (PV), and gas separation (GS).

The market size and application range of gas separation using a membrane is expanding day by day, because it can reduce energy consumption and operating costs. For example, in the petrochemical process, propylene and ethylene are separated by using a distillation process, which is economically inefficient because energy consumption is very high. In particular, a separation membrane using a polymer film has the advantage of selectively separating a specific gas from a gas mixture according to a difference in the permeation rate of various gas molecules. Polymer membranes for gas separation have been studied a lot since the permeation characteristics of polymers were reported by Mitchell (1830, 1833), Graham (1866), and the like. Mitchell observed that a natural rubber balloon filled with hydrogen gas shrinks with time, and he hypothesized that this phenomenon was due to the release or permeation of gas through the balloon wall. Graham proved Mitchell's assumption through repeated experiments using natural rubber film, and published the first quantitative measurement method for gas permeation rate through natural rubber film.

Despite such a long history, polymer membranes have only been applied to the gas separation industry for only about 40 years. The dense polymer membrane that could be manufactured before the 1970s could not have the high permeate flow rate required for practical application because it was too thick. The development of the Loeb-Sourirajan process was a milestone in the history of membranes that made it possible to manufacture defect-free, high-flow, ultra-thin, asymmetric reverse osmosis membranes. Afterwards, many polymer membranes and modules based on asymmetric membranes were developed and started to be applied to treatment systems in microfiltration, ultrafiltration and reverse osmosis fields.

In the 1980s, the first commercial-scale gas separation membrane system using a polymer membrane called Prism was introduced, and it began to be used in the hydrogen recovery process from the purge gas in the ammonia synthesis plant. In the existing process, ammonia was produced through the reaction of hydrogen and nitrogen under a catalytic reaction at high temperature and pressure. Hydrogen is supplied through the steam reforming reaction of natural gas, and since the ammonia conversion rate is limited to 18-20%, unreacted gas must be recovered and re-supplied toward the raw material in order to improve the yield. The gas is purged to prevent mixing of the inert gas and unreacted methane. This purge gas contains hydrogen, but the existing separation process has a disadvantage in that the cost for recovering hydrogen is high. The gas separation membrane is most preferable when the feed gas is high pressure and the permeate section can be maintained at low pressure, and can be applied to this process.

Currently, gas separation processes using polymer membranes are constantly competing with other separation processes such as adsorption, absorption, and deep cooling. The gas separation membrane process has excellent competitiveness compared to other technologies due to its easy operation, small scale, low energy consumption, mobility, reliability, and space efficiency. Currently, the gas separation membrane process is used for the separation and recovery of hydrogen from petrochemical processes and synthesis gas. Other applications include EOR (Enhanced Oil Recovery), natural gas refining, landfill gas recovery, air separation, dehydration, degassing, and helium. It is applied to recovery.

In order to overcome the limitations of existing polymer membranes, a nanoparticle/polymer composite membrane (MMM) manufacturing technology in which nanoparticles capable of molecular sieve function are mixed in a polymer matrix is being studied. However, in order for the separation membrane-based process to compete with the existing separation process such as absorption/adsorption, it is necessary to further improve the performance of the composite membrane. In particular, it is very difficult to find the optimal nanoparticle/polymer combination among numerous nanoparticle candidates. has a hard problem. Accordingly, when the concentration of nanoparticles in the nanoparticle/polymer composite separator is increased, the permeability is increased but the selectivity is lowered. Therefore, it is necessary to develop a composite separator capable of solving this problem.

Korean Patent Publication No. 10-1394396

An object of the present invention is to solve the above problems, and a composite polymer separator capable of improving the separation performance of the composite separator by artificially controlling defects inside the metal organic structure (MOF) added to the composite polymer separator, and a method for manufacturing the same is about

According to one aspect of the present invention,

polymer membrane material; and

Dispersed in the polymer membrane material, a metal-organic framework (MOF) nanoparticles of which defects are controlled; a composite polymer membrane comprising a separation membrane is provided.

The metal-organic framework (MOF) nanoparticles in which the defects are controlled may be those in which defects are induced in the metal-organic framework by adding a monocarboxylic acid-based compound when the metal-organic framework (MOF) nanoparticles are manufactured.

The monocarboxylic acid-based compound may be represented by R-COOH, and R may be -CF ₃ , -CCl ₃ , or a C1 to C10 alkyl group.

The monocarboxylic acid compound may be trifluoroacetic acid.

Based on the total weight of the composite polymer separator, the content of the metal-organic framework (MOF) nanoparticles in which the defects are controlled may be 10 to 50 wt%.

The polymer membrane material may be any one series selected from polyimide, polysulfone, cellulose acetate, polycarbonate, perfluoropolymer, siloxane polymer, and polyacetylene polymer.

The polymer membrane material may be any one series selected from polyimide or polysulfone.

The polyimide-based polymer membrane material is 6FDA-DAM, 6FDA-DAM-OH, PIM-6FDA-OH, 6FDA-6FpDA, 6FDA-DABA, Matrimid, 6FDA-6FpDA: DABA copolymer, and 6FDA-DAM: DABA public It may be any one selected from coalescing.

The metal-organic framework (MOF) is UiO-66, MFU-4l, ZIF-8, MIL-53, MIL-100, MIL-101, MIL-96, MIL-100, CALF-25, CAU -10, DUT-51, DUT-67, FMOF-1, MIL-100, MIL-101, MIL-125, MIL-127, MOF-525, MOF-545, MOF-801, MOF-802, MOF-804 , MOF-841, Ni-NIC, NU-1000, PCN-225, PCN-222, PCN-224, and may be any one selected from SCUTC-18.

The composite polymer membrane may be for any one membrane selected from carbon dioxide capture, natural gas purification, petrochemical distillation process, hydrogen purification process, water purification treatment, and reverse osmosis seawater desalination.

The composite polymer separator may be used in any one selected from electronic devices, electrodes, packaging, and sensors.

According to another aspect of the present invention,

(a) Metal-organic framework (MOF) in which defects are controlled by inducing defects in the internal structure of metal-organic structures by reacting metal precursors, organic ligands, water and monocarboxylic acid-based compound additives in an organic solvent (Metal-organic framework, MOF) preparing nanoparticles; and

(b) the step of complexing the polymer membrane material and the metal-organic framework (MOF) nanoparticles in which the defects are controlled; is provided a method for manufacturing a composite polymer membrane comprising a.

In step (a),

The molar equivalent ratio of the metal precursor and the monocarboxylic acid-based compound additive may be 1:5 to 1:40.

in step (b).

The defect-controlled metal-organic framework (MOF) nanoparticles may be included in an amount of 10 to 50 wt% based on the total weight of the composite polymer separator.

Metal ions included in the metal precursor are Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁺ , Pt ²⁺ , Pt ⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵ It may be any one selected from ⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ .

The organic ligand is benzene-1,4-dicarboxylic acid (benzene-1,4-dicarboxylic acid), benzene-1,3,5-tricarboxylic acid (benzene-1,3,5-tricarboxylic acid), 2-methylimidazole, ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, phthalic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 1H-1,2,3-triazole (1H-1,2,3- triazole), 1H-1,2,4-triazole (1H-1,2,4-triazole) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (3,4-dihydroxy- 3-cyclobutene-1,2-dione) may be any one selected from.

According to another aspect of the present invention,

A gas separation system including the composite polymer membrane is provided.

According to another aspect of the present invention,

A water treatment system including the composite polymer membrane is provided.

The composite polymer separation membrane comprising the defect-controlled nanoparticles of the present invention artificially creates a defect by synthesizing it using an additive in the manufacture of a metal-organic framework (MOF), and thus the manufactured defect is controlled. By complexing nanoparticles with a polymer membrane, gas permeability can be improved while maintaining selectivity, thereby remarkably improving separation performance compared to a composite polymer membrane incorporating nanoparticles. In addition, since it can be applied to various polymer membrane materials, it can be applied to various separation processes, namely, carbon dioxide capture technology before and after combustion (carbon dioxide/nitrogen), natural gas refining (carbon dioxide/methane), petrochemical process (olefin/paraffin), hydrogen refining It can be used in various processes such as technology and reverse osmosis seawater desalination technology and can show the effect of energy saving.

1 is a schematic diagram of a polymer membrane according to an embodiment of the present invention.
2 is a SEM image of UiO-66 nanoparticles according to a preparation example of the present invention.
3 is an XRD analysis result according to Experimental Example 1.
4 is a BET analysis result according to Experimental Example 1.
5 is an isothermal adsorption line according to Experimental Example 1.
6 is an SEM image of a composite polymer separator according to Experimental Example 2.
7 is a measurement result of the physical properties of the composite polymer membrane according to Experimental Example 2.
8 is a gas separation performance evaluation result according to the UiO-66 nanoparticle defect concentration of Experimental Example 3.
9 is C ₃ H ₆ /C ₃ H ₈ according to the type of polymer matrix of Experimental Example 4 This is the separation performance evaluation result.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily carry out the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that detailed descriptions of related known techniques may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is used only to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, but is one or more other features or It should be understood that the possibility of the presence or addition of numbers, steps, acts, elements, or combinations thereof is not precluded in advance.

Hereinafter, the composite polymer membrane of the present invention will be described.

The composite polymer membrane of the present invention includes a polymer membrane material; and metal-organic framework (MOF) nanoparticles dispersed in the polymer membrane material and having a controlled defect.

The metal-organic framework (MOF) nanoparticles in which the defects are controlled may be those in which defects are induced in the metal-organic framework by adding a monocarboxylic acid-based compound when the metal-organic framework (MOF) nanoparticles are manufactured.

The monocarboxylic acid-based compound additive may interfere with particle growth during the manufacture of a metal-organic structure (MOF) to form a bond within the structure.

The monocarboxylic acid-based compound is represented by R-COOH, wherein R is -CF ₃ , -CCl ₃ , or a C1 to C10 alkyl group. More preferably, R is -CF ₃ or -CCl ₃ , and even more preferably, the monocarboxylic acid-based compound may be trifluoroacetic acid.

Based on the total weight of the composite polymer separator, the content of the metal-organic framework (MOF) nanoparticles with controlled defects is preferably 10 to 50 wt%, more preferably 15 to 45 wt%, even more Preferably, it may be 20 to 40 wt%. If it is less than 10 wt %, the effect of improving the transmittance is not sufficient, and if it exceeds 50 wt %, the durability of the composite polymer separator may be deteriorated, and it may be difficult to maintain selectivity.

The polymer membrane material may be any one series selected from polyimide, polysulfone, cellulose acetate, polycarbonate, perfluoropolymer, siloxane polymer, and polyacetylene polymer, preferably polyimide or polysulfone series can

More preferably, the polyimide-based polymer membrane material is 6FDA-DAM, 6FDA-DAM-OH, PIM-6FDA-OH, 6FDA-6FpDA, 6FDA-DABA, Matrimid, 6FDA-6FpDA: DABA copolymer, and 6FDA -DAM: It may be any one selected from DABA copolymers, but the scope of the present invention is not limited thereto, and various polymer membrane materials capable of exhibiting interfacial stability by complexing with a metal-organic structure may be applied.

The metal-organic framework (MOF) is UiO-66, MFU-4l, ZIF-8, MIL-53, MIL-100, MIL-101, MIL-96, MIL-100, CALF-25, CAU -10, DUT-51, DUT-67, FMOF-1, MIL-100, MIL-101, MIL-125, MIL-127, MOF-525, MOF-545, MOF-801, MOF-802, MOF-804 , MOF-841, Ni-NIC, NU-1000, PCN-225, PCN-222, PCN-224, SCUTC-18, etc. can be applied.

Preferably, any one MOF selected from UiO-66, ZIF-8, MIL-53, MIL-101, MIL-125, MOF-801, and Ni-NTC, which has an oxygen functional group and has an attractive force with the polymer matrix, may be used. can

The composite polymer membrane may be used for any one membrane selected from carbon dioxide capture, natural gas purification, petrochemical distillation process, hydrogen purification process, water purification, and reverse osmosis seawater desalination.

The composite polymer separator may be used in any one selected from electronic devices, electrodes, packaging, and sensors.

Hereinafter, a method for manufacturing the composite polymer membrane of the present invention will be described.

First, metal-organic framework (MOF) nano-structures in which defects are controlled by inducing defects in the internal structure of metal-organic structures by reacting metal precursors, organic ligands, water, and monocarboxylic acid-based compound additives in an organic solvent Particles are prepared (step a).

The molar equivalent ratio of the metal precursor and the monocarboxylic acid compound additive is preferably 1:5 to 1:40, more preferably 1:10 to 1:40, even more preferably 1:20 to 1:40. , most preferably 1:30 to 1:40. If the monocarboxylic acid-based compound additive is less than the lower limit, the defect formation of the metal-organic structure may be insufficient, and the effect of improving the permeability of the composite polymer separator finally manufactured may be reduced. may not be able to support

Metal ions included in the metal precursor are Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁺ , Pt ²⁺ , Pt ⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵ It may be any one selected from ⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ , preferably Zr ⁴⁺ . This is because because it has a high oxidation number, it can form complexes with a number of ligands, and thus has high thermal, physical, and chemical stability, thereby facilitating the control of defects in the structure.

The organic ligand is benzene-1,4-dicarboxylic acid (benzene-1,4-dicarboxylic acid), benzene-1,3,5-tricarboxylic acid (benzene-1,3,5-tricarboxylic acid), 2-methylimidazole, ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, phthalic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 1H-1,2,3-triazole (1H-1,2,3- triazole), 1H-1,2,4-triazole (1H-1,2,4-triazole) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (3,4-dihydroxy- 3-cyclobutene-1,2-dione), preferably benzene-1,4-dicarboxylic acid or benzene-1,3,5- It may be a tricarboxylic acid (benzene-1,3,5-tricarboxylic acid), because it can form a complex with Zr ⁴⁺ , so that it is easy to control defects in the structure.

Next, the polymer membrane material and the metal-organic framework (MOF) nanoparticles in which the defects are controlled are complexed (step b).

The defect-controlled metal-organic framework (MOF) nanoparticles are preferably included in 10 to 50 wt% based on the total weight of the composite polymer separator, more preferably 15 to 40 wt%, even more Preferably, it can be complexed to contain 20 to 40 wt%. If it is less than 10wt%, the effect of increasing the permeability of the composite polymer membrane may be insufficient, and if it exceeds 40wr%, the durability of the composite polymer membrane may be deteriorated, and it may be difficult to maintain selectivity.

The present invention provides a gas separation system including the above-described composite polymer membrane.

In addition, the present invention provides a water treatment system including the above-described composite polymer membrane.

Hereinafter, examples according to the present invention will be described in detail.

[Example]

Preparation Example 1: Synthesis of UiO-66 nanoparticles (UiO-TF6) with controlled defects

UiO-66 nanoparticles are a type of metal-organic framework (MOF). They have high specific surface area (~1,000 m ² /g), molecular-level pore size (6.0 Å), and high thermal and chemical stability. is a substance

First, 0.862 g of zirconium chloride (ZrCl ₄ ), 0.615 g of H ₂ BDC (benzene-1,4-dicarboxylic acid) as an organic ligand, 0.2 g of water, and 2.531 g of trifluoroacetic acid (TFA) as an additive in DMF The solvent was added to 94.4 g and stirred at 70 °C. In other words, the molar equivalent ratio of ZrCl ₄ , H ₂ BDC, water, TFA, and DMF is 1:1:3:6:350.

Next, the solution obtained by annealing in a convection oven at 120° C. for 72 hours was centrifuged to obtain a white slurry. Thereafter, the white slurry was overnight in a vacuum oven at 70° C. to obtain UiO-66 nanoparticles.

Preparation Example 2: Synthesis of UiO-66 nanoparticles (UiO-TF12) with controlled defects

UiO-66 in which defects were controlled under the same conditions as in Preparation Example 1 except that 5.064 g of trifluoroacetic acid (TFA) was added and the molar equivalent ratio of ZrCl ₄ and TFA was 1:12 instead of 1:6 Nanoparticles were synthesized.

Preparation Example 3: Synthesis of UiO-66 nanoparticles (UiO-TF36) with controlled defects

UiO-66 in which defects were controlled under the same conditions as in Preparation Example 1 except that 15.190 g of trifluoroacetic acid (TFA) was added and the molar equivalent ratio of ZrCl ₄ and TFA was 1:36 instead of 1:6 Nanoparticles were synthesized.

Comparative Preparation Example 1: Synthesis of UiO-66 nanoparticles

UiO-66 nanoparticles were synthesized under the same conditions as in Preparation Example 1 except that trifluoroacetic acid (TFA) was not added.

SEM images of UiO-66 nanoparticles prepared according to Preparation Examples 1 to 3 and Comparative Preparation Example 1 are shown in FIG. 2 .

Example 1-1: Composite Separation Membrane Containing Defect Controlled UiO-66 Nanoparticles

Using an ultrasonic disperser to add the defect-controlled UiO-66 nanoparticles prepared according to Preparation Example 1 to the 6FDA-DAM matrix represented by the following Chemical Formula 1, which is a polyimide-based polymer, which is a gas separation membrane material, at a concentration of 20 wt% After dispersing in a solvent for 1 hour, a composite separator was prepared by adding a polymer to prepare and casting a polymer/UiO-66/solvent mixed solution.

[Formula 1]

Example 1-2: Composite Separation Membrane Containing Defect Controlled UiO-66 Nanoparticles

prepared according to Preparation Example 2 instead of Preparation Example 1 A composite separator was prepared under the same conditions as in Example 1-1 except that UiO-66 nanoparticles were used.

Example 1-3: Composite Separator Containing Defect Controlled UiO-66 Nanoparticles

Prepared according to Preparation Example 3 instead of Preparation Example 1 A composite separator was prepared under the same conditions as in Example 1-1 except that UiO-66 nanoparticles were used.

Example 1-4: Composite Separator Containing Defect Controlled UiO-66 Nanoparticles

A composite separator was prepared under the same conditions as in Example 1-1, except that 40 wt% of UiO-66 nanoparticles were included instead of 20 wt%.

Comparative Example 1: Composite Separation Membrane Containing UiO-66 Nanoparticles

Prepared according to Comparative Preparation Example 1 instead of Preparation Example 1 A composite separator was prepared under the same conditions as in Example 1-1 except that UiO-66 nanoparticles were used.

Example 2: Composite Membrane Containing Defect Controlled UiO-66 Nanoparticles

A composite separator was prepared under the same conditions as in Example 1-3, except that a PIM-6FDA-OH polymer matrix annealed at 250° C. represented by the following Chemical Formula 2 was used instead of the 6FDA-DAM matrix.

[Formula 2]

Example 3: Composite Separation Membrane Containing Defect Controlled UiO-66 Nanoparticles

A composite separator was prepared under the same conditions as in Example 1-3, except that a Matrimid polymer matrix represented by the following Chemical Formula 3 was used instead of the 6FDA-DAM matrix.

[Formula 3]

Example 4: Composite Membrane Containing Defect Controlled UiO-66 Nanoparticles

A composite separator was prepared under the same conditions as in Example 1-3, except that a polysulfone (PSf) polymer matrix represented by the following Chemical Formula 4 was used instead of the 6FDA-DAM matrix.

[Formula 4]

A schematic diagram of the preparation of the polymer composite separator into which the nanoparticles with controlled defects according to Examples 1 to 4 were introduced is shown in FIG. 1 .

Comparative Example 1: Pure 6FDA-DAM Membrane

A separation membrane was prepared only with a 6FDA-DAM matrix without complexing UiO-66 nanoparticles.

Comparative Example 2: Composite Separation Membrane Containing UiO-66 Nanoparticles

A composite separator was prepared under the same conditions as in Example 1-1, except that UiO-66 nanoparticles except for the additive of Comparative Preparation Example 1 were used instead of the binding-controlled UiO-66 nanoparticles of Preparation Example 1.

Comparative Example 3: Composite Separation Membrane Containing UiO-66 Nanoparticles

A composite separator was prepared under the same conditions as in Comparative Example 2, except that 40 wt% of UiO-66 nanoparticles were included instead of 20 wt%.

Comparative Example 4: Pure PIM-6FDA-OH

A separator was prepared only with a PIM-6FDA-OH matrix without complexing UiO-66 nanoparticles.

Comparative Example 5: Composite Separation Membrane Containing UiO-66 Nanoparticles

A composite polymer membrane was prepared under the same conditions as in Comparative Example 2, except that a PIM-6FDA-OH matrix was used instead of 6FDA-DAM.

Comparative Example 6: Pure Matrimid

A separator was prepared only with a Matrimid matrix without complexing UiO-66 nanoparticles.

Comparative Example 7: Composite Separation Membrane Containing UiO-66 Nanoparticles

A composite polymer membrane was prepared under the same conditions as in Comparative Example 2, except that a Matrimid matrix was used instead of 6FDA-DAM.

Comparative Example 8: Pure Matrimid

A separator was prepared only with a polysulfone matrix without complexing UiO-66 nanoparticles.

Comparative Example 9: Composite Separation Membrane Containing UiO-66 Nanoparticles

A composite polymer membrane was prepared under the same conditions as in Comparative Example 2, except that a polysulfone matrix was used instead of 6FDA-DAM.

[Experimental example]

Experimental Example 1: Structural analysis of defect-controlled UiO-66 nanoparticles

The structure of UiO-66 synthesized according to Preparation Examples 1 to 3 and Comparative Preparation Example 1 was confirmed through X-ray diffraction analysis (XRD) analysis, and the results are shown in FIG. 3 . (a) is an XRD spectrum, (b) is an XRD spectrum in the low 2θ region (2-8°). According to this, the XRD peak appeared to rise in the low 2θ region, confirming that Reo phase defects, that is, ligand defects (missing linker) and metal-organism cluster defects (missing cluster) increased.

In addition, BET analysis results of UiO-66 nanoparticles prepared according to Preparation Examples 1 to 3 and Comparative Preparation Example 1 are shown in FIG. 4 , (a) is a BET isothermal adsorption/desorption line, (b) is a micropore (Micropore) This is the measurement result of the pore distribution in the region, and the results of the specific surface area analysis are summarized in Table 1 below.

division BET surface area (m ² /g) UiO (Comparative Preparation Example 1) 868 UiO-TF6 (Preparation Example 1) 1125 UiO-TF12 (Preparation Example 2) 1344 UiO-TF36 (Preparation Example 3) 1411

According to this, the specific surface area of the UiO-66 nanoparticles was 868, 1125, 1344, and 1411 m ² /g for the UiO-66 nanoparticles of Preparation Examples 1 to 3 and Comparative Preparation Example 1, respectively, and the additive trifluoro There was a tendency to increase as the concentration of acetic acid (TF) increased, that is, as the number of defects inside the UiO-66 nanoparticles increased. On the other hand, UiO-66 prepared according to Preparation Examples 1 to 4 and Comparative Preparation Example 1 The isothermal adsorption line of the nanoparticles is shown in FIG. 5 . (a) is an isothermal adsorption line for carbon dioxide, and (b) is an isothermal adsorption line for nitrogen. According to this, UiO-66 nanoparticles with controlled defects showed higher adsorption amounts of carbon dioxide and nitrogen as the concentration of the additive increased, that is, as the number of defects increased.

Experimental Example 2: Analysis of Structure and Physical Properties of Polymer Separation Membrane

SEM images of (a) the pure 6FDA-DAM membrane of Comparative Example 1 and (b) the 6FDA-DAM composite membrane of Example 1-3 are shown in FIG. 6 .

In addition, (a) XRD spectrum of the composite separator prepared according to Examples 1-1 to 1-3, the pure 6FDA-DAM separator of Comparative Example 1, and the 6FDA-DAM composite separator prepared according to Comparative Example 2, ( b) FT-IR spectrum, (c) elastic modulus according to temperature, (d) tan δ value and glass transition temperature (T _g ) measurement results according to temperature are shown in FIG. 7 .

According to this, it was found that the 6FDA-DAM composite separators prepared according to Examples 1-1 to 1-3, respectively, formed a uniform nanoparticle/polymer interface regardless of the defect degree of UiO-66.

Experimental Example 3: Gas separation performance evaluation according to the UiO-66 nanoparticle defect concentration

The gas separation performance according to the UiO-66 nanoparticle defect concentration of the prepared composite membrane was evaluated under the conditions of a single gas, a pressure difference of 2 bar, a temperature of 35° C., and a membrane area of 1.13 cm ² The results are shown in FIG. 8 and Table 2. . Here, (a) H ₂ /N ₂ separation performance, (b) CO ₂ /N ₂ separation performance, (c) O ₂ /N ₂ separation performance, (d) C ₃ H ₆ /C ₃ H ₈ separation performance analysis Results, black dots are pure 6FDA-DAM membranes of Comparative Example 1, red dots are 6FDA-DAM composite membranes containing UiO-66 nanoparticles with controlled defects of Examples 1-1 to 1-3, black solid lines are polymers It represents the upper limit of the permeability-selectivity of the separation membrane.

separator Comparative Example 1 Comparative Example 2 Example 1-1 Example 1-2 Examples 1-3 Item Permeabilty (Barrer) H ₂ 556 1207 1728 2368 3162 CO ₂ 595 1358 2249 2697 3470 O ₂ 113 273 453 549 699 N ₂ 30.7 78.5 130 161 208 C ₃ H ₆ 21.4 81 127 184 242 C ₃ H ₈ 2.0 8.5 12.1 18.8 25.1 Item Ideal Selectivity (-) O ₂ /N ₂ 3.7 3.5 3.5 3.4 3.4 CO ₂ /N ₂ 19.4 17.6 17.3 16.9 16.7 H ₂ /N ₂ 18.2 15.6 13.3 14.8 15.2 C ₃ H ₆ /C ₃ H ₈ 10.3 9.8 10.6 9.8 9.7

According to this, as a result of evaluating the gas separation performance of the UiO-66/6FDA-DAM composite membranes prepared according to Examples 1-1 to 1-3, the higher the defect concentration of the added UiO-66 nanoparticles, the higher the gas permeability. It was found that the selectivity was maintained without lowering even when In particular, the UiO-66/6FDA-DAM composite separator prepared according to Examples 1-1 to 1-3, respectively, has only improved transmittance up to 10 times or more compared to the pure polymer matrix (6FDA-DAM) of Comparative Example 1. However, since the selectivity is maintained, it can be seen that the separation performance is significantly higher when compared with the performance index of the existing polymer material for gas separation. The composite membrane of the present invention is not limited to a specific gas and is expected to be widely used in applications such as hydrogen purification, carbon dioxide capture, nitrogen loading, and olefin/paraffin separation.

When MOF nanoparticles such as UiO-66 nanoparticles are complexed with a membrane polymer, gas permeability can be increased by increasing the concentration of MOF nanoparticles. Increasing the concentration did not improve the separation performance of the polymer membrane. However, the composite separator of the present invention is characterized in that the selectivity is maintained without lowering the selectivity while increasing the permeability by adjusting the content of the monocarboxylic acid-based additive while optimizing and fixing the concentration of the MOF nanoparticles to 20 wt%. have.

Experimental Example 4: C according to the type of polymer matrix ₃ H ₆ /C ₃ H ₈ Separation performance evaluation

The C ₃ H ₆ /C ₃ H ₈ separation performance according to the UiO-66 nanoparticle defect concentration of the composite separator using various polymer matrices was evaluated under the conditions of a single gas, a pressure difference of 2 bar, a temperature of 35℃, and a membrane area of 1.13 cm ² . The results are shown in FIG. 9 and Table 3.

polymer matrix separator C ₃ H ₆ Permeability (Barrer) C ₃ H ₆ /C ₃ H ₈ Single gas selectivity (-) 6FDA-DAM Comparative Example 1 (pure polymer) 21 10.3 Comparative Example 2 (+ UiO-66 20 wt%) 87 9.8 Comparative Example 3 (+ UiO-66 40 wt%) 147 8.9 Examples 1-3 (+ D-UiO-66 20 wt%) 237 9.7 Examples 1-4 (+ D-UiO-66 40 wt%) 350 9.4 PIM-6FDA-OH Comparative Example 4 (pure polymer) 4.2 25.9 Comparative Example 5 (+ UiO-66 20 wt%) 8.8 22.5 Example 2 (+ D-UiO-66 20 wt%) 22.1 20.8 Matrimid Comparative Example 6 (pure polymer) 0.09 12.1 Comparative Example 7 (+ UiO-66 20 wt%) 0.19 11.9 Example 3 (+ D-UiO-66 20 wt%) 0.33 10.5 Polysulfone (PSf) Comparative Example 8 (pure polymer) 0.04 1.1 Comparative Example 9 (+ UiO-66 20 wt%) 0.07 1.4 Example 4 (+ D-UiO-66 20 wt%) 0.29 4.7

According to this, since the present invention is not limited to a specific polymer matrix and exhibits an effect of improving the separation performance at the same level in various polymer matrices, it can be seen that the optimal composite separator design incorporating the present invention can be flexibly performed.

In the above, although embodiments of the present invention have been described, those of ordinary skill in the art can add, change, delete or add components within the scope that does not depart from the spirit of the present invention described in the claims. The present invention may be variously modified and changed by, etc., and this will also be included within the scope of the present invention.

Claims (15)

polymer membrane material; and
Dispersed in the polymer membrane material, and a defect-controlled metal-organic framework (MOF) nanoparticles;
The polymer membrane material is any one series selected from polyimide, polysulfone, cellulose acetate, polycarbonate, perfluoropolymer, siloxane polymer, and polyacetylene polymer,
The defect-controlled metal-organic structure (MOF) nanoparticles are UiO-66 in which the defects induced in the metal-organic structure are controlled by adding a monocarboxylic acid-based compound when manufacturing the metal-organic structure nanoparticles,
The monocarboxylic acid-based compound is represented by R-COOH, wherein R is -CF ₃ , -CCl ₃ , or C1 to C10 H ₂ /N ₂ , CO ₂ /N ₂ , O ₂ / N ₂ , or C ₃ H ₆ /C ₃ H ₈ Composite polymer membrane for gas separation. delete delete According to claim 1,
The monocarboxylic acid-based compound is a composite polymer membrane, characterized in that the trifluoroacetic acid (Trifluoroacetic acid). According to claim 1,
Based on the total weight of the composite polymer membrane, the content of the metal-organic framework (MOF) nanoparticles with controlled defects is 10 to 50 wt%. delete According to claim 1,
The polyimide-based polymer membrane material is 6FDA-DAM, 6FDA-DAM-OH, PIM-6FDA-OH, 6FDA-6FpDA, 6FDA-DABA, Matrimid, 6FDA-6FpDA: DABA copolymer, and 6FDA-DAM: DABA public Composite polymer membrane, characterized in that any one selected from the coal. delete (a) Metal-organic framework (MOF) in which defects are controlled by inducing defects in the internal structure of metal-organic structures by reacting metal precursors, organic ligands, water, and monocarboxylic acid-based compound additives in an organic solvent (Metal-organic framework, MOF) preparing nanoparticles; and
(b) complexing the polymer membrane material and the metal-organic framework (MOF) nanoparticles in which the defects are controlled;
The metal ion contained in the metal precursor is Zr ⁴⁺ ,
The defect-controlled metal organic structure (MOF) nanoparticles are defect-controlled UiO-66,
The organic ligand is benzene-1,4-dicarboxylic acid,
The monocarboxylic acid-based compound is represented by R-COOH, wherein R is -CF ₃ , -CCl ₃ , or C1 to C10 H ₂ /N ₂ , CO ₂ /N ₂ of claim 1, characterized in that it is an alkyl group. O ₂ /N ₂ , or C ₃ H ₆ /C ₃ H ₈ A method of manufacturing a composite polymer membrane for gas separation. 10. The method of claim 9,
In step (a),
The method for producing a composite polymer membrane, characterized in that the molar equivalent ratio of the metal precursor and the monocarboxylic acid compound additive is 1:5 to 1:40. 10. The method of claim 9,
in step (b).
The method for manufacturing a composite polymer membrane, characterized in that the defect-controlled metal-organic framework (MOF) nanoparticles are included in an amount of 10 to 50 wt% based on the total weight of the composite polymer membrane. delete delete A gas separation system comprising the composite polymer membrane of any one of claims 1, 4, 5 and 7. delete

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