KR20220046034A - Microporous polymer fiber adsorbent, adsorption module including microporous polymer fiber adsorbent, organic pollutant removal system using adsorption module including microporous polymer fiber adsrobent - Google Patents

Abstract

In one embodiment of the present invention, provided is a microporous polymer fiber adsorbent which consists of a polymer with intrinsic microporosity, which is a polymer containing micropores, wherein the polymer with intrinsic microporosity is a fiber type and has a hierarchical pore structure in which pores having different sizes from the micropores are interconnected.

Description

MICROPOROUS POLYMER FIBER ADSORBENT, ADSORPTION MODULE INCLUDING MICROPOROUS POLYMER FIBER ADSORBENT, ORGANIC POLLUTANT SYSTEM USING ADSORPTION MODULE INCLUDING MICROPOROUS POLYMER FIBER ADSROBENT}

The present invention relates to an organic pollutant removal system that adsorbs and desorbs specific substances using a microporous polymer fiber adsorbent, an adsorption module comprising a microporous polymer fiber adsorbent, and an adsorption module comprising a microporous polymer fiber adsorbent.

Methods such as combustion, catalytic combustion, adsorption, membrane separation, and condensation are used as a treatment technique for mixed materials including organic pollutants such as volatile organic compounds. Among them, the adsorption technology is widely used because it can collect various types of organic pollutants at once and recover them at a high concentration.

One of the problems to be solved by the present invention is an adsorbent with improved adsorption and removal efficiency of various organic pollutants such as volatile organic compounds from mixed materials, a module including the adsorbent, and an organic pollutant including a module including the adsorbent To provide a material removal system.

The microporous polymer fiber adsorbent according to embodiments of the present invention is made of an intrinsic microporous polymer that is a polymer containing micropores, and the intrinsic microporous polymer is a fiber type. and has a hierarchical pore structure in which the micropores and pores having different sizes are interconnected.

The adsorption module including the microporous polymer fiber adsorbent according to the embodiments of the present invention is made of an intrinsic microporous polymer that is a polymer containing micropores, and the intrinsic microporous polymer is a fiber ( A housing body in the form of a fiber) in which a plurality of microporous polymer fiber adsorbents having a hierarchical structure in which the micropores and pores of different sizes are interconnected and the plurality of microporous polymer fiber adsorbents are uniformly stacked; A housing having an inlet formed at one end of the housing body and through which the mixed material is introduced, and an outlet formed at the other end of the housing body and discharged after contaminants are adsorbed from the mixed material by the plurality of microporous polymer fiber adsorbents. include

An organic pollutant separation system according to embodiments of the present invention includes a first adsorption module, a second adsorption module, and a vacuum pump connected to the first adsorption module and the second adsorption module, wherein the first adsorption module and each of the second adsorption modules is made of an intrinsic microporous polymer that is a polymer containing micropores, and the intrinsic microporous polymer is made of a fiber type, and the micropores are A plurality of microporous polymer fiber adsorbents having a hierarchical structure in which pores and pores having different sizes are interconnected, and a housing body in which the plurality of microporous polymer fiber adsorbents are uniformly stacked, are formed at one end of the housing body and mixed material a housing having this inlet and an outlet formed at the other end of the housing body and discharged after contaminants are adsorbed from the mixed material by the plurality of microporous polymer fiber adsorbents, in the first adsorption module , the mixed material is introduced into the inlet of the first adsorption module, the contaminants are adsorbed by the microporous polymer fiber adsorbent, and the adsorption process of discharging the material from which the contaminants are removed through the outlet of the first adsorption module is performed, , while the adsorption process is performed in the first adsorption module, an adsorbent regeneration process of desorbing the adsorbed contaminants from the microporous polymer fiber adsorbent is performed in the second adsorption module.

According to an embodiment of the present invention, by using a microporous polymer fiber adsorbent made of PIMs (Polymer of Intrinsic Microporosity) containing micropores of 2 nm or less, specific contaminants included in the mixed materials can be effectively adsorbed.

Various and advantageous advantages and effects of the present invention are not limited to the above, and will be more easily understood in the course of describing specific embodiments of the present invention.

1 is a molecular model of PIM-1 among PIMs capable of forming a microporous polymer fiber adsorbent according to an embodiment of the present invention.
2 is a graph showing the adsorption amount of an adsorbent composed of PIM-1, Zeolite Y, and ZSM-5, respectively.
3 is a graph showing a breakthrough curve of a module filled with a microporous fiber adsorbent according to an embodiment of the present invention.
4 is a graph showing a pressure drop between a module filled with a microporous fiber adsorbent and a module filled with a powder adsorbent according to an embodiment of the present invention.
5 is a graph of a desorption experiment of a microporous fiber adsorbent to which an organic material is adsorbed.
6 is a schematic perspective view of a microporous polymer fiber adsorbent according to an embodiment of the present invention.
7 is a schematic perspective view of a microporous polymer fiber adsorbent according to an embodiment of the present invention.
8 is a scanning electron microscope (SEM) photograph of the microporous polymer fiber adsorbent according to an embodiment of the present invention.
9 is a schematic perspective view of a microporous polymer fiber adsorbent according to an embodiment of the present invention.
10 is a scanning electron microscope (SEM) photograph of the microporous polymer fiber adsorbent according to an embodiment of the present invention.
11 is a schematic perspective view of a microporous polymer fiber adsorbent according to embodiments of the present invention.
12 is a scanning electron microscope (SEM) photograph of a microporous polymer fiber adsorbent according to an embodiment of the present invention.
13A and 13B are graphs showing breakthrough curves of a module filled with a microporous fiber adsorbent according to an embodiment of the present invention.
14 is a schematic perspective view of a microporous polymer fiber adsorbent according to embodiments of the present invention.
15 is a ternary phase equilibrium diagram for PIM-1, a solvent, and a non-solvent forming a microporous polymer fiber adsorbent according to an embodiment of the present invention.
16A is a schematic perspective view of an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention.
FIG. 16B is a diagram illustrating a flow of a mixed material in an adsorption module including a microporous polymer fiber adsorbent according to the embodiment of FIG. 16A .
17A is a schematic perspective view of an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention;
FIG. 17B is a diagram illustrating a flow of a mixed material in an adsorption module including a microporous polymer fiber adsorbent according to the embodiment of FIG. 17A .
18A to 18C are block diagrams of an organic pollutant removal system using an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention.
19A and 19B are block diagrams of an organic pollutant removal system using an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention.
20A and 20B are block diagrams of an organic pollutant removal system using an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

The microporous polymer fiber adsorbent according to embodiments of the present invention may be made of a polymer with intrinsic microporosity (PIM), which is a polymer containing micropores of about 2 nm or less. The micropores contained in the intrinsically microporous polymer can adsorb a specific organic material relatively well in the mixed material. The organic material adsorbed by the micropores of the intrinsically microporous polymer is, for example, a volatile organic compound (Volatile) such as benzene and toluin discharged from various industries including semiconductor industry, wastewater treatment plant, petrochemical, and paint. Organic Compounds, VOC) or hydrocarbons (THC). The microporous polymer fiber adsorbent may include an inherently microporous polymer in the form of a fiber. The intrinsically microporous polymer may improve chemical stability by performing post-treatment such as chemical/thermal cross-linking treatment.

The intrinsically microporous polymer is, for example, PIM-1, PIM-7, PIM-SBF-1, PIM-SBF-2, PIM-SBF-3, PIM-SBF-4, PIM-SBF-5, PIM -EA-TB, PIM-PI-EA, PIM-Trip-TB, TPIM-1, PIM-MP-TB, PIM-EA-TB, PIM-Trip-TB, PIM-1-AO (amidoxime-functionalized PIM- 1), PIM-TZ (tetrazole-substituted PIMs), PIM-TMN-Trip, PIM-Btrip, KAUST-PI-1, CF ₃ -ROMP, etc. may be formed, but is not limited thereto. In an exemplary embodiment, the inherent microporous polymer may be PIM-1 represented by the following Chemical Formula 1, and the like.

[Formula 1]

In Formula 1, n is a natural number of at least 2 or more.

Microporous fiber adsorbents made of intrinsically microporous polymers have low moisture sensitivity and can be stable even in strong acids and bases. In addition, it is easy to manufacture a desired product shape by dissolving it in a solution and drying it to form it. Accordingly, the microporous polymer fiber adsorbent according to an embodiment of the present invention has various shapes including monolithic, monolith, and hollow fiber types described in FIGS. 6 to 14 . can make The microporous polymer fiber adsorbent made of the intrinsically microporous polymer may have a hierarchical pore structure formed by interconnecting micropores and pores having different sizes. Specifically, the microporous fiber adsorbent is formed by interconnecting mesopores or macropores that may occur during the process of manufacturing the intrinsic microporous polymer in the form of fibers and the micropores embedded in the intrinsic microporous polymer. It may have a hierarchical pore structure.

1 is a molecular model of PIM-1 among intrinsic microporous polymers capable of forming a microporous polymer fiber adsorbent according to an embodiment of the present invention. As shown in FIG. 1 , the intrinsically microporous polymer including PIM-1 has a rigid contorsion and may have micropores in the molecular structure itself because it is not densely stacked on a solid phase.

2 is a graph showing the adsorption amount of an adsorbent composed of PIM-1, Zeolite Y, and ZSM-5, respectively.

Isopropyl alcohol (IPA) adsorption amount of the adsorbent composed of PIM-1, Zeolite Y, and ZSM-5 zeolite, respectively, increases as the pressure increases, and the microporous fiber adsorbent composed of PIM-1 at a pressure of 35 mmHg The adsorption amount of isopropyl alcohol of isopropyl alcohol is about 6 mmol/g, which can be about 3 times greater than that of an adsorbent made of hydrophobic ZSM-5 zeolite, and about 1.5 times greater than that of an adsorbent made of Zeolite Y. . As such, an adsorbent made of an inherently microporous polymer including embedded micropores may have a large adsorption amount of organic materials such as volatile organic compounds (VOC) or hydrocarbons (THC) at relatively the same pressure.

3 is a graph showing the breakthrough curve of a module filled with a microporous fiber adsorbent.

Referring to FIG. 3 , when isopropyl alcohol (IPA) is injected into the module filled with the microporous fiber adsorbent according to an embodiment of the present invention, the amount of isopropyl alcohol (IPA) adsorbed to the module can be checked. there is. The adsorption amount can be obtained through the difference in the integral value when the control (Blank) and isopropyl alcohol (IPA) are injected, and it can be seen that the adsorption amount is in the range of about 0.8 to 0.9 mmol/g.

3 is a graph showing that a gas containing 1000 ppm of isopropyl alcohol (IPA) was injected at 50 sccm into a module made of PIM-1 and filled with a monolithic microporous fiber adsorbent according to an embodiment of the present invention; Therefore, it can be confirmed that isopropyl alcohol (IPA) is not discharged until about 5000 seconds when gas is injected. In addition, it can be seen that isopropyl alcohol (IPA) is adsorbed to the module filled with the microporous fiber adsorbent until about 20000 seconds after the start of gas injection.

4 is a graph showing the pressure drop between a module filled with a microporous fiber adsorbent and a module filled with a powder-type adsorbent.

In the graph of FIG. 4 , when gas is introduced into the module Y filled with the adsorbent in powder form, the pressure drop is higher than when gas is introduced into the module X filled with the fibrous microporous fiber adsorbent. It can be seen that is large. In addition, when gas is introduced into the module Y filled with the adsorbent in powder form, it can be seen that the pressure drop is relatively sharply increased as the superficial velocity increases. In contrast, in the module (X) filled with the microporous fiber adsorbent according to the embodiments of the present invention, the pressure drop is very low at a superficial speed of about 15 m/s or less, and the increase in the pressure drop is relatively low even at a superficial speed of 15 m/s or more. small things can be identified. When the module is filled with the adsorbent in powder form, the gas movement space inside the bed is narrow and the pressure drop is large, whereas the module filled with the microporous fiber adsorbent according to the embodiments of the present invention is as described in FIGS. 16b and 17b. , the pressure drop can be relatively small because the movement of the gas is uniform across the inside of the bed.

5 is a graph of a desorption experiment of a microporous fiber adsorbent to which an organic material is adsorbed.

According to the graph of Figure 5, when nitrogen at 120 °C is injected at 50 sccm in a module including a microporous fiber adsorbent to which isopropyl alcohol (IPA) is adsorbed, isopropyl alcohol (IPA) desorbed after about 500 seconds detection can be confirmed. It can be seen that the emission concentration of the desorbed isopropyl alcohol (IPA) increases from about 500 seconds to about 1000 seconds, and then decreases and the desorption is completed in about 2000 seconds.

As such, in the adsorbent regeneration process described in FIGS. 18c, 19b, and 20b, the microporous fiber adsorbent according to the embodiments of the present invention is stable at about 350 ° C or less, so that the adsorbed by injecting a gas above a certain temperature The process of regenerating the adsorbent by desorbing the material may be stably performed.

microporous polymer fiber adsorbent; first embodiment

6 is a schematic perspective view of a microporous polymer fiber adsorbent according to an embodiment of the present invention.

Referring to FIG. 6 , the microporous polymer fiber adsorbent 10a according to an embodiment of the present invention may have a monolithic shape. The microporous polymer fiber adsorbent 10a may have a cylindrical shape. In an exemplary embodiment, the cross-section in the horizontal direction of the microporous polymer fiber adsorbent 10a may be circular, but is not limited thereto, and may have various shapes such as an oval or a crushed oval.

The microporous polymer fiber adsorbent 10a may include mesopores 1 or macropores 3 interconnected with micropores to form a hierarchical pore structure. The mesopores (1) or macropores (3) may be formed during the manufacturing process of making the intrinsic microporous polymer fibrous. 6, the microporous polymer fiber adsorbent 10a may contain mesopores 1 in the range of about 2 nm to about 50 nm or macropores 3 in the range of about 50 nm or more in the surface and cross-section. can In an exemplary embodiment, the macropores 3 may range from about 0.05 μm to 5 μm. In an exemplary embodiment, the microporous polymer fiber adsorbent 10a contains micropores of about 2 nm or less and mesopores 1 in the range of about 2 nm to 50 nm, and may not contain macropores 3 of about 50 nm or more. there is. Since the microporous polymer fiber adsorbent 10a is made of an inherently microporous polymer having micropores in the molecule itself, the adsorption rate of contaminants including volatile organic compounds in the mixed material can be increased by the micropores. By means of the mesopores 1 or macropores 3 having a larger diameter than the diameter of the micropores and forming a hierarchical structure with the micropores, the microporous polymer fiber adsorbent 10a is used to transfer the adsorbed material to the micropores or Heat transfer and the like may be easy. The hierarchical pore structure of the microporous polymer fiber adsorbent 10a in which the materials rapidly transferred by the mesopores 1 or macropores 3 that facilitate mass transfer are adsorbed by the micropores increases the adsorbent utilization rate. can

7 is a schematic perspective view of a microporous polymer fiber adsorbent according to an embodiment of the present invention. Referring to FIG. 7 , the microporous polymer fiber adsorbent 10b according to an embodiment of the present invention may have a monolith shape. 7 , the microporous polymer fiber adsorbent 10b may have a honeycomb-shaped cross section, but is not limited thereto. For example, the cross-section of the monolithic microporous polymer fiber adsorbent 10b may be in a form in which a plurality of circles are clustered. In the monolithic form, mixed materials move to a space formed in the form of a honeycomb, etc., thereby increasing the adsorption utilization rate.

8 is a scanning electron microscope (SEM) photograph of the microporous polymer fiber adsorbent according to an embodiment of the present invention. Fig. 8 (a) is a cross-section of the microporous polymer fiber adsorbent in monolithic form, Fig. 8 (b) is an enlarged cross-section of the microporous polymer fiber adsorbent in monolithic form, and Fig. 8 (c) is a monolithic form This is the result of observing the surface of the microporous polymer fiber adsorbent.

Referring to FIG. 8( a ), it can be seen that the microporous polymer fiber adsorbent is formed in a monolithic form. Referring to the enlarged cross-sectional view of FIG. 8B , it can be seen that mesopores 1 having a range of about 0.002 μm to 0.05 μm are formed. It can be seen that mesopores are formed on the surface of FIG. 8(c) as in the cross section. The mesopores observed in FIGS. 8(b) and 8(c) may be interconnected with nano-scale micropores, and may act as a connection path for the mixed material.

microporous polymer fiber adsorbent; second embodiment

9 is a schematic perspective view of a microporous polymer fiber adsorbent according to an embodiment of the present invention.

Referring to FIG. 9 , the microporous polymer fiber adsorbent 20 according to an embodiment of the present invention may have a hollow fiber shape. That is, the microporous polymer fiber adsorbent 20 may have a hollow cylindrical shape. The microporous polymer fiber adsorbent 20 in the form of a hollow fiber, similar to the first embodiment, is made of an inherent microporous polymer and contains micropores, and mesopores (1) or macropores (3) interconnected with the micropores ) to form a hierarchical pore structure.

10 is a scanning electron microscope (SEM) photograph of the microporous polymer fiber adsorbent according to an embodiment of the present invention. 10 (a) is a cross-section of the microporous polymer fiber adsorbent in the form of a hollow fiber, FIG. 10 (b) is an enlarged cross-section of the microporous polymer fiber adsorbent in the form of a hollow fiber, and FIG. This is the result of observing the surface of the polymer fiber adsorbent.

Referring to FIG. 10( a ), it can be seen that the microporous polymer fiber adsorbent is formed in the form of a hollow fiber. Referring to the enlarged cross-sectional view of FIG. 10(b) , it can be seen that mesopores 1 having a range of 0.002 μm to 0.05 μm are formed. It can be seen that mesopores are formed on the surface of FIG. 10(c). Similar to the monolithic microporous polymer fiber adsorbent, the hollow fiber microporous polymer fiber adsorbent including the intrinsic microporous polymer may include mesopores (1).

microporous polymer fiber adsorbent; third embodiment

11 is a schematic perspective view of a microporous polymer fiber adsorbent according to an embodiment of the present invention.

Referring to FIG. 11 , the microporous polymer fiber adsorbent 30 having a monolithic shape includes an intrinsic microporous polymer containing micropores and a separate nanoporous material 5 dispersed in the intrinsic microporous polymer. can The nanoporous material 5 is a carbon-based adsorbent, zeolite, metal-organic frameworks (MOFs), covalent organic frameworks (COF), and conjugated microporous polymers. ) may be at least one of Various contaminants may be adsorbed to the microporous polymer fiber adsorbent 30 according to the type of the nano-porous material 5 . When the nano-porous material 5 is dispersed, contaminants are adsorbed into the micro-pores of the nano-porous material 5 in addition to the micro-pores contained in the inherent micro-porous polymer. Adsorption of the material may be achieved.

12 is a scanning electron microscope (SEM) photograph of a microporous polymer fiber adsorbent according to an embodiment of the present invention. Figure 12 (a) is a cross section of the microporous polymer fiber adsorbent in which Zeolite Y is dispersed, Figure 12 (b) is an enlarged cross section of the microporous polymer fiber adsorbent in which Zeolite Y is dispersed, and Figure 12 (c) is Zeolite Y dispersed. This is the result of observing the enlarged cross section at high magnification of the microporous polymer fiber adsorbent.

Referring to FIG. 12 , a separate nanoporous material dispersed in the microporous polymer fiber adsorbent can be identified.

13A and 13B are graphs showing breakthrough curves of a module filled with a microporous fiber adsorbent according to an embodiment of the present invention.

13A and 13B show a gas containing 1000 ppm of isopropyl alcohol (IPA) in a module made of PIM-1 and filled with a monolith-type microporous fiber adsorbent in which Zeolite Y is dispersed, according to an embodiment of the present invention. Corresponds to the graph showing the injection at 50 sccm. 13a is a graph for a module filled with a microporous fiber adsorbent in which 25 wt% of Zeolite Y is dispersed, and FIG. 13b is a graph for a module filled with a microporous fiber adsorbent in which 50 wt% of Zeolite Y is dispersed.

In FIG. 13a, the module filled with the microporous fiber adsorbent in which 25wt% of Zeolite Y is dispersed has faster adsorption than the module filled with the microporous fiber adsorbent composed only of PIM-1 in the monolith form described with reference to FIG. can check that Through the graph, it can be seen that the adsorption amount of the module filled with the microporous fiber adsorbent in which 25 wt% of Zeolite Y is dispersed is in the range of about 0.75 to 0.9 mmol/g.

In FIG. 13b, the module filled with the microporous fiber adsorbent in which 50 wt% of Zeolite Y is dispersed has faster adsorption than the module filled with the microporous fiber adsorbent composed only of PIM-1 in the monolith form described with reference to FIG. can check that It can be seen that the module according to the embodiment of FIG. 13B has a larger adsorption amount than the module according to the embodiment of FIG. 13A . Through the graph of FIG. 13b, it can be seen that the adsorption amount of the module filled with the microporous fiber adsorbent in which 50 wt% of Zeolite Y is dispersed is in the range of about 1.1 to 1.3 mmol/g.

14 is a schematic perspective view of a microporous polymer fiber adsorbent according to an embodiment of the present invention. Referring to FIG. 14 , the microporous polymer fiber adsorbent 40 having a hollow fiber shape may include an intrinsic microporous polymer containing micropores and a separate nanoporous material 5 dispersed in the intrinsic microporous polymer. there is. The description of the nanoporous material may be applied in the same manner as described with reference to FIG. 11 .

Method for manufacturing microporous polymer fiber adsorbent

Forming a dope solution by dissolving an intrinsic microporosity (PIM), a polymer containing micropores that selectively adsorbs only a specific substance in a mixed material, in a solvent, the intrinsic micropores It may comprise the step of forming a microporous polymer fiber adsorbent with the spinning stock solution comprising the porous polymer.

In the step of forming the spinning dope, the solvent may be, for example, Tetrahydrofuran (THF), chloroform, dichloromethane, or the like. A spinning dope may be formed by dissolving an intrinsically microporous polymer, which is a polymer containing micropores of 2 nm or less, in the solvent. An inherently microporous polymer having a composition capable of dissolving in a solvent to form a spinning dope can be selected. The intrinsically microporous polymer may be, for example, PIM-1.

15 is a ternary phase equilibrium diagram for PIM-1, a solvent, and a non-solvent forming a microporous polymer fiber adsorbent according to an embodiment of the present invention. Referring to FIG. 15 , in the step of forming the spinning dope, a spinning dope may be formed with the respective compositions of PIM-1 forming A phase, a solvent, and a non-solvent. Binodal line (L) divides the region forming the A phase and B phase. In an exemplary embodiment, a cost comprising about 75 wt% to about 85 wt% of THF solvent, 5 wt% to 35 wt% of PIM-1, dimethylacetamide (DMAc) or ethanol (EtOH) to form phase A, in an exemplary embodiment The hawk may range from 10 wt % to 25 wt %.

In an exemplary embodiment, in the step of forming the spinning dope, only PIM is dissolved in a solvent to form a spinning dope for preparing the microporous polymer fiber adsorbents 10a, 10b, and 20 as shown in FIGS. 6, 7, and 9. . In another embodiment, an inherently microporous polymer is dissolved in a solvent, and a spinning dope in which the nanoporous material 5 shown in FIGS. 11 and 14 is dispersed may be formed.

In the step of spinning the spinning dope to form the microporous polymer fiber adsorbent, the spinning dope can be spun through various spinning methods such as dry-jet wet quench spinning, electrospinning, and centrifugal force spinning. there is. In the spinning step of forming the microporous polymer fiber adsorbent, depending on the method of use of the adsorbent, various forms including the monolithic, monolithic, and hollow fiber forms described above may be spun.

Adsorption module with microporous polymer fiber adsorbent

16A is a schematic perspective view of an adsorption module including a microporous polymer fiber adsorbent according to an embodiment of the present invention. FIG. 16B is a diagram illustrating a flow of mixed materials in an adsorption module including a microporous polymer fiber adsorbent according to the embodiment of FIG. 16A .

Referring to FIG. 16A , the adsorption module 100a may include a plurality of monolithic microporous polymer fiber adsorbents 10a of FIG. 6 . The adsorption module 100a includes a housing body 110 having an internal space for accommodating the microporous polymer fiber adsorbent 10a, an inlet 120 through which the mixed material is introduced, and a plurality of microporous polymer fiber adsorbents 10a. It may include a housing including an outlet 130 that is discharged after the contaminants are adsorbed from the mixed material. The inlet 120 may be formed at one end of the housing body 110 , and the outlet 130 may be formed at the other end of the housing body 110 opposite to the end at which the inlet is formed. Monolithic microporous polymer fiber adsorbents 10a each having a similar size and shape may be uniformly stacked on the housing body 110 to efficiently fill the inside of the adsorption module 100a. When the microporous polymer fiber adsorbents are uniformly filled in the housing body 110 , the mixed material that has not been able to adsorb and remove contaminants in the adsorption module 100a passes through the housing body 110 and goes out to the outlet 130 . It can prevent you from going out. By adjusting the packing density of the microporous polymer fiber adsorbents 10a in the adsorption module 100a, the differential pressure and the adsorption amount of the mixed material introduced through the inlet 120 may be adjusted. In an exemplary embodiment, the adsorption module 100a may include the microporous polymer fiber adsorbent 10b in the monolith form of FIG. 7 .

Referring to FIG. 16B , when the mixed gas flows into the adsorption module 100a including the microporous polymer fiber adsorbent 10a, contaminants are adsorbed from the inlet gas G1 by the microporous polymer fiber adsorbent 10a - After being removed (E) and contaminants are adsorbed to the outlet 130 , the gas G1 ′ may be discharged. In the adsorption module 100a comprising the microporous polymer fiber adsorbent 10a in a monolithic form, the inlet gas G1 flows through the uniformly stacked microporous polymer fiber adsorbent 10a, and has a hierarchical pore structure Since the contaminants are adsorbed to the intrinsic microporous polymer by the intrinsic microporous polymer, the gas moves uniformly across the inside of the bed, and as shown in the graph of FIG. 4 , the pressure drop may be relatively small. In addition, specific substances are adsorbed-removed in such a way that the inlet gas G1 flows through the uniformly stacked microporous polymer fiber adsorbents 10a, thereby preventing a decrease in the adsorption throughput of the inlet gas G1.

17A is a schematic perspective view of an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention; FIG. 17B is a diagram illustrating a flow of a mixed material in an adsorption module including a microporous polymer fiber adsorbent according to the embodiment of FIG. 17A . In FIG. 17A , descriptions of the same components denoted by the same reference numerals as in FIG. 16A will be omitted, and only modified components will be described.

Referring to FIG. 17A , the adsorption module 100b may include the microporous polymer fiber adsorbent 20 in the form of a plurality of hollow fibers of FIG. 9 . By uniformly stacking the microporous polymer fiber adsorbents 10b in the form of hollow fibers of similar size and shape on the housing body 110, the inside of the adsorption module 100a can be efficiently filled.

Referring to FIG. 17B , when the mixed gas flows into the adsorption module 100b including the microporous polymer fiber adsorbent 10b, the inlet gas flows along the outside of the microporous polymer fiber adsorbent 20 in the form of a hollow fiber. It can be divided into (G2) and a gas (G3) flowing through the hollow space formed in the center of the cylindrical microporous polymer fiber adsorbent in the form of a hollow fiber. The gas (G2) flowing along the outside of the microporous polymer fiber adsorbent 20 in the form of a hollow fiber absorbs and removes contaminants by a hierarchical pore structure such as mesopores interconnected with micropores embedded in the intrinsic microporous polymer. E) and can be discharged (G2'). The gas (G3) flowing through the hollow space formed in the cylindrical center of the microporous polymer fiber adsorbent 20 may be discharged by adsorbing and removing contaminants from the empty space to the adsorbent (G3'). In the adsorption module 100b including the microporous polymer fiber adsorbent 10b in the form of a hollow fiber, the inlet gases G2 and G3 pass through the microporous polymer fiber adsorbents 10b uniformly stacked inside and outside the hollow fiber. Since contaminants are adsorbed to the intrinsic microporous polymer by the hierarchical pore structure, the gas flows uniformly across the inside of the bed, so that the pressure drop can be relatively small, as shown in the graph of FIG. 4 .

Organic pollutant removal system using adsorption module with microporous polymer fiber adsorbent

18A to 20B are block diagrams of an organic pollutant removal system using an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention. By forming an organic pollutant removal system using at least one adsorption module according to exemplary embodiments of the present invention, pollutants in exhaust gas, pollutants in wastewater treatment, or ultra pure water (UPW) in semiconductor processes ), organic compounds, etc. can be removed during production. In the exemplary embodiments described in FIGS. 18A to 20C , the size of the adsorption modules and the number of connected modules may be variously changed according to the required processing capacity of organic compounds and the like. In exemplary embodiments, the connection method of the adsorption modules may be selected and changed in parallel or series type according to the size and operation method of the equipment used.

18A to 18C are exhaust gas treatment systems 1100 using an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention.

18A to 18C , the exhaust gas treatment system 1100 is connected to the first adsorption module 101 , the second adsorption module 102 , the first adsorption module 101 and the second adsorption module 102 . It may include a vacuum pump 200 and a condenser 300 to be. Each of the first adsorption module 101 and the second adsorption module 102 may be an adsorption module including a plurality of microporous polymer fiber adsorbents described with reference to FIGS. 16A to 17B .

18A shows the adsorption process P1 performed by the first adsorption module 101 in the exhaust gas treatment system 1100 . First, the exhaust gas corresponding to the mixed material may be introduced into the inlet 120a of the first adsorption module 101 by opening the first valve (a). In the exhaust gas flowing into the first adsorption module 101, contaminants are adsorbed by the microporous polymer fiber adsorbent included in the housing body of the first adsorption module 101, and the pollutants are removed from the first adsorption module. It may be discharged to the outlet (130a) of (101). At this time, the second valve (b) may be opened to allow the purified gas to move, and the remaining valves except for the first and second valves (a, b) may be closed. When the first adsorption module 101 performs the adsorption process P1 as described above, the second adsorption module 102 may be in a standby state.

18B shows the adsorption process P1 performed by the second adsorption module 102 in the exhaust gas treatment system 1100 . First, by opening the third valve c, the exhaust gas corresponding to the mixed material may be introduced into the inlet 120b of the second adsorption module 102 . In the exhaust gas flowing into the second adsorption module 102, contaminants are adsorbed by the microporous polymer fiber adsorbent included in the housing body of the second adsorption module 102, and the contaminants are removed from the second adsorption module. It can be discharged to the outlet (130b) of (102). At this time, the purified gas may move by opening the fourth valve d, and the remaining valves except for the third and fourth valves c and d may be closed. Contrary to that described in FIG. 18A , when the adsorption process P1 as described above is performed in the second adsorption module 102 , the first adsorption module 101 may be in a standby state. That is, the individual adsorption process performance and atmosphere of one or more modules on the system can be controlled, respectively.

FIG. 18C shows an adsorption process P1 performed by the second adsorption module 102 in the exhaust gas treatment system 1100, an adsorbent regeneration process P2 performed in the first adsorption module 101, and non-condensed pollutants shows the resorption process P3 through the second module 102 of

The adsorption process P1 may be performed in the second adsorption module 102 in the same manner as described with reference to FIG. 18B . In the first adsorption module 101, after the adsorption process as shown in FIG. 18A is performed, the adsorbent regeneration process P2 may be performed. The adsorbent regeneration process P2 of the first adsorption module 101 may be performed simultaneously with the adsorption process P1 of the second adsorption module 102 . In the adsorbent regeneration process (P2), heat is applied from the outside of the first adsorption module 101, or it is connected to a vacuum pump 200 to create a vacuum state. It may refer to the process of desorbing contaminants from the microporous polymer fiber adsorbent. The pollutants desorbed from the first adsorption module 101 may be condensed through the condenser 300 by opening the fifth valve (e). By the condenser 300 , the contaminants may be recovered and treated in a liquid phase. In this case, contaminants not condensed by the condenser 300 among the contaminants desorbed in the first adsorption module 101 may remain. The non-condensed pollutants may be returned to the exhaust gas inlet and re-injected into the first adsorption module 101 to perform a re-adsorption process P3 . As such, in the organic pollutant treatment system, one or more adsorption modules 101 and 102 may simultaneously perform a treatment process, thereby increasing efficiency. In example embodiments, the adsorption process P1 and the resorption process P3 may be performed in the first adsorption module 101 , and the adsorbent regeneration process P2 may be performed in the second adsorption module 102 . .

19A and 19B are a wastewater treatment system 1200 using an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention.

19A and 19B , the wastewater treatment system 1200 may include a first adsorption module 101 , a second adsorption module 102 , and a vacuum pump 200 . In FIGS. 19A and 19B , descriptions of the same components as those described with reference to FIGS. 18A to 18C are omitted.

19A shows the adsorption process P1 performed by the first adsorption module 101 in the wastewater treatment system 1200 . 19A , wastewater corresponding to the mixed material may be introduced into the inlet 120a of the first adsorption module 101 by opening the first valve (a). In the wastewater flowing into the first adsorption module 101, contaminants are adsorbed-removed by the microporous polymer fiber adsorbent included in the housing body of the first adsorption module 101, and the outlet 130a of the first adsorption module 101 is ) can be released. The purified water from which the contaminants have been removed can be discharged into rivers.

The wastewater treatment system 1200 of FIG. 19b is similar to the exhaust gas treatment system 1100 of FIG. 13b , the adsorption process P1 performed by the second adsorption module 102 and the first adsorption module 101 performed The adsorbent regeneration process P2 is shown.

When the wastewater adsorption process (P1) is performed in the second adsorption module 102, the first adsorption module 101 desorbs the contaminants adsorbed on the microporous polymer fiber adsorbent from the microporous polymer fiber adsorbent. P2) can be performed. In the wastewater treatment system 1200 , the adsorbent regeneration process P2 may desorb contaminants by applying heat to the first adsorption module 101 .

20A and 20B are views of a water treatment system 1300 for producing ultrapure water (UPW) using an adsorption module including a microporous polymer fiber adsorbent according to embodiments of the present invention. The water treatment system 1300 is a system for adsorbing-removing organic matter and dissolved gas to make UPW (ultra-pure water), which is water used in a semiconductor process.

20A and 20B , the water treatment system 1300 may include a first adsorption module 101 , a second adsorption module 102 , and a vacuum pump 200 . In FIGS. 20A and 20B , descriptions of the same components as those described with reference to FIGS. 18A to 18C are omitted.

FIG. 20A shows the adsorption process P1 performed by the first adsorption module 101 in the water treatment system 1300 . By opening the first valve (a), water including dissolved gas and organic matter may be introduced into the inlet 120a of the first adsorption module 101 . 20a and 20b, the mixture is shown as TOC or gas, but is not limited thereto. In the water introduced into the first adsorption module 101, contaminants such as dissolved gas and organic matter are adsorbed by the microporous polymer fiber adsorbent included in the housing body of the first adsorption module 101, and the contaminants are removed. It may be discharged to the outlet 130a of the first adsorption module 101 . At this time, the purified water may move by opening the second valve (b).

The water treatment system 1300 of FIG. 20B is similar to the exhaust gas treatment system 1100 of FIG. 18B , the adsorption process P1 performed by the second adsorption module 102 and the first adsorption module 101 performed in The adsorbent regeneration process (P2) is shown.

In FIG. 20B , by opening the third valve c, water including dissolved gas and organic matter may be introduced into the inlet 120b of the second adsorption module 102 . Contaminants such as dissolved gas and organic matter are adsorbed to the water introduced into the second adsorption module 102 by the microporous polymer fiber adsorbent included in the housing body of the second adsorption module 101, and the contaminants are removed. It may be discharged to the outlet 130b of the second adsorption module 102 . At this time, the purified water may move by opening the fourth valve (d). The adsorbent regeneration process P2 may be performed in the first adsorption module 101 simultaneously with the adsorption process P1 of the second adsorption module 102 . In the adsorbent regeneration process (P2), heat is applied from the outside of the first adsorption module 101, or a vacuum pump 200 connected to the upper portions of the first and second adsorption modules is connected to create a vacuum state. ) may refer to a process of desorbing contaminants adsorbed to the microporous polymer fiber adsorbent from the microporous polymer fiber adsorbent. As such, in the water treatment system 1300, one or more modules may simultaneously perform a treatment process, thereby increasing efficiency.

The present invention is not limited by the above-described embodiments and the accompanying drawings, but is intended to be limited by the appended claims. Therefore, various types of substitution, modification and change will be possible by those skilled in the art within the scope not departing from the technical spirit of the present invention described in the claims, and it is also said that it falls within the scope of the present invention. something to do.

10a, 10b, 20, 30, 40: microporous polymer fiber adsorbent
100a, 100b: adsorption module
1100, 1200, 1300: organic pollutant separation system

Claims (10)

It is composed of Polymer with Intrinsic Microporosity, which is a polymer containing micropores.
The inherent microporous polymer is made of a fiber type,
A microporous polymer fiber adsorbent having a hierarchical pore structure in which the micropores and pores having different sizes are interconnected.
According to claim 1,
The intrinsically microporous polymer is a microporous polymer fiber adsorbent having one of a monolithic (Monolithic), a monolith (Monolith), and a hollow fiber (Hollow fiber) form.
According to claim 1,
The hierarchical pore structure is a microporous polymer fiber adsorbent comprising mesopores interconnected with the micropores.
4. The method of claim 3,
and wherein the hierarchical pore structure includes macropores interconnected with the micropores.
According to claim 1,
The microporous polymer fiber adsorbent further comprising a separate nano-porous material dispersed in the intrinsic microporous polymer.
6. The method of claim 5,
The nano-porous material is a carbon-based adsorbent, zeolite (Zeolite), metal-organic frameworks (Metal-Organic Frameworks, MOFs), covalent organic framework (COF), and conjugated microporous polymer (Conjugated microporous polymer) at least one microporous polymer fiber adsorbent.
According to claim 1,
The intrinsically microporous polymer is PIM-1, PIM-7, PIM-SBF-1, PIM-SBF-2, PIM-SBF-3, PIM-SBF-4, PIM-SBF-5, PIM-EA-TB, PIM-PI-EA, PIM-Trip-TB, TPIM-1, PIM-MP-TB, PIM-EA-TB, PIM-Trip-TB, PIM-1-AO (amidoxime-functionalized PIM-1), PIM- Microporous polymer fiber adsorbent consisting of one of tetrazole-substituted PIMs (TZ), PIM-TMN-Trip, PIM-Btrip, KAUST-PI-1, and CF ₃ -ROMP
It consists of a polymer with Intrinsic Microporosity, which is a polymer containing micropores, and the intrinsic microporous polymer is made of a fiber type, and the micropores and pores having different sizes have different sizes. a plurality of microporous polymer fiber adsorbents having an interconnected hierarchical structure; and
A housing body in which the plurality of microporous polymer fiber adsorbents are uniformly stacked, an inlet formed at one end of the housing body and through which a mixed material is introduced, and formed at the other end of the housing body, by the plurality of microporous polymer fiber adsorbents An adsorption module comprising a microporous polymer fiber adsorbent including a housing having an outlet through which the contaminants are adsorbed from the mixed material and discharged.
a first adsorption module;
a second adsorption module; and
A vacuum pump connected to the first adsorption module and the second adsorption module,
Each of the first adsorption module and the second adsorption module is made of an intrinsic microporosity polymer that is a polymer containing micropores, and the intrinsic microporous polymer is a fiber type. a plurality of microporous polymer fiber adsorbents having a hierarchical structure in which the micropores and pores having different sizes are interconnected; and
A housing body in which the plurality of microporous polymer fiber adsorbents are uniformly stacked, an inlet formed at one end of the housing body and through which a mixed material is introduced, and formed at the other end of the housing body, by the plurality of microporous polymer fiber adsorbents and a housing having an outlet through which contaminants are adsorbed from the mixed material and discharged;
In the first adsorption module, the mixed material is introduced into the inlet of the first adsorption module, the contaminants are adsorbed by the microporous polymer fiber adsorbent, and the material from which the contaminants are removed is discharged through the outlet of the first adsorption module adsorption process is carried out,
An adsorbent regeneration process for desorbing the adsorbed pollutants from the microporous polymer fiber adsorbent is performed in the second adsorption module while the adsorption process is performed in the first adsorption module.
10. The method of claim 9,
further comprising a condenser,
Contaminants desorbed from the microporous polymer fiber adsorbent are recovered in a liquid phase through the condenser, and non-condensed contaminants among the desorbed contaminants are re-injected into the first adsorption module to perform a resorption process. separation system.

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