KR20230089417A - Integral hybrid reducing device using separation membrane and hybrid reducing method using the same - Google Patents

Abstract

Embodiments of the present disclosure provide an integrated composite reduction device including a reduction cartridge including a first reduction module for separating water and hydrophilic VOCs and a second reduction module for separating hydrophobic VOCs, thereby providing excellent VOC reduction efficiency, It is possible to provide an integrated composite reduction device capable of efficient space utilization and cost reduction and a composite reduction method using the same.

Description

Integrated composite reduction device using separation membrane and composite reduction method using the same {INTEGRAL HYBRID REDUCING DEVICE USING SEPARATION MEMBRANE AND HYBRID REDUCING METHOD USING THE SAME}

Embodiments of the present disclosure relate to an integrated composite reduction device using a separator and a composite reduction method using the same.

VOC (Volatile organic compound) is used as a general term for all organic substances that exist in a gaseous state at room temperature and pressure. VOCs can act as precursors that form photochemical oxides as secondary pollutants such as ozone that are harmful to humans and animals and plants by causing photochemical reactions with nitrogen oxides (NO _X ) in the air. These VOCs are emitted from most industrial sites, but among them, painting facilities are the largest emission source, accounting for about 34% of the total amount of VOCs generated in Korea.

VOCs emitted from painting facilities are characterized by containing dust and moisture, and most painting facilities remove VOCs by wet cleaning at the bottom. Even in general painting facilities that do not adopt the wet cleaning method, the annual average relative humidity in Korea is high at 67%, and the average relative humidity in summer is very high at 74%, so there is a lot of moisture. This water inflow is reduced due to the relatively diluted VOC concentration as the exhaust gas throughput increases, and competitive interactions between water molecules and VOC occur or VOC molecules are desorbed from the surface of the treated material by moisture. The removal efficiency is reduced.

In addition, technologies capable of treating VOCs include biological treatment, thermal treatment, adsorption treatment, and membrane treatment, and the most commonly used treatment methods include thermal treatment and adsorption treatment. The heat treatment process is an advantageous technology when the concentration of VOC is relatively high, and the process is simple and the installation cost is low. The adsorption treatment process is applied to various processes because of the advantage of being able to treat VOC emitted into the atmosphere most easily, but the operating cost increases rapidly when the concentration is high, the efficiency decreases over time, and the problem of excessive renewable energy for the adsorbent is pointed out as a disadvantage. there is.

Since the VOC treatment technology using a membrane is manufactured using a material that has a higher affinity for VOC than air, VOC dissolves on the surface of the membrane faster than other gases and diffuses rapidly within the membrane. Permeation occurs according to the theory.

However, in a process with high humidity, the VOC treatment efficiency is reduced, and a swelling phenomenon occurs due to VOC and moisture, which may reduce the VOC removal efficiency. In addition, problems such as a rapid decrease in performance may occur due to degradation of the separator material by the organic solvent VOC.

In order to solve the above problems, the inventors of the present disclosure invented an integrated composite reduction device using a separator and a composite reduction method using the same.

Embodiments of the present disclosure provide an integrated composite reduction device having excellent chemical resistance to VOC.

Embodiments of the present disclosure provide an integrated composite reduction device capable of efficient space utilization and cost reduction accordingly.

Embodiments of the present disclosure provide a composite reduction method with excellent moisture and VOC reduction efficiency.

Embodiments of the present disclosure may provide an integrated composite reduction device including an inlet, a reduction cartridge, and an outlet.

The reduction cartridge includes a first reduction module and a second reduction module. The first reduction module includes hydrophilic nanoparticles. The second reduction module includes hydrophobic nanoparticles.

Embodiments of the present disclosure may provide a complex reduction method including a gas supply step, a first reduction step, a second reduction step and a gas discharge step.

The gas supply step is a step in which gas is supplied to the gas supply unit. The first reduction step is a step in which moisture and hydrophilic VOC of the supplied gas are reduced. The second reduction step is a step in which hydrophobic VOCs in the supplied gas are reduced. The gas discharge step is a step in which the gas purified through the first reduction step and the second reduction step is discharged from the gas discharge unit.

According to embodiments of the present disclosure, by using hydrophilic nanoparticles and hydrophobic nanoparticles, it is possible to provide an integrated composite reduction device having excellent chemical resistance to VOC.

According to embodiments of the present disclosure, since water and hydrophilic VOCs and hydrophobic VOCs are reduced at the same time, it is possible to efficiently utilize space and provide an integrated composite reduction device capable of reducing costs accordingly.

According to embodiments of the present disclosure, by using a first reduction module for reducing water and hydrophilic VOC and a second reduction module for reducing hydrophobic VOC, it is possible to provide a composite reduction method with excellent VOC reduction efficiency.

1 is a view showing an integrated composite reduction device according to embodiments of the present disclosure.
Figure 2 is a view showing an integrated composite reduction device according to another embodiment of the present disclosure.
3 is a view showing a reduction cartridge and a vacuum line according to embodiments of the present disclosure.
4 is a view showing the first reduction module of FIG. 3 .
5 is a view showing an example of the first separator of FIG. 4 .
6 is a partial cross-sectional view of an example of the first separator of FIG. 5 .
FIG. 7 is a partial cross-sectional view of another example of the first separator of FIG. 5 .
8 is a view showing the second reduction module of FIG. 3 .
9 is a view showing the second separator of FIG. 8 .
10 is a partial cross-sectional view of an example of the second separator of FIG. 9 .
11 is a view showing a coating step of a separator according to embodiments of the present disclosure.
12 is a view showing the structure of the separator prepared according to FIG. 11.

DETAILED DESCRIPTION Some embodiments of the present disclosure are described in detail below with reference to exemplary drawings. In adding reference numerals to components of each drawing, the same components may have the same numerals as much as possible even if they are displayed on different drawings. In addition, in describing the present disclosure, when it is determined that a detailed description of a related known configuration or function may obscure the gist of the present disclosure, the detailed description may be omitted. When "comprises", "has", "consists of", etc. mentioned in this specification is used, other parts may be added unless "only" is used. In the case where a component is expressed in the singular, it may include the case of including the plural unless otherwise explicitly stated.

Also, terms such as first, second, A, B, (a), and (b) may be used in describing the components of the present disclosure. These terms are only used to distinguish the component from other components, and the nature, sequence, order, or number of the corresponding component is not limited by the term.

In the description of the positional relationship of components, when it is described that two or more components are "connected", "coupled" or "connected", the two or more components are directly "connected", "coupled" or "connected". ", but it will be understood that two or more components and other components may be further "interposed" and "connected", "coupled" or "connected". Here, other components may be included in one or more of two or more components that are “connected”, “coupled” or “connected” to each other.

In the description of the temporal flow relationship related to components, operation methods, production methods, etc., for example, "after", "continued to", "after", "before", etc. Alternatively, when a flow sequence relationship is described, it may also include non-continuous cases unless “immediately” or “directly” is used.

On the other hand, when a numerical value or corresponding information (eg, level, etc.) for a component is mentioned, even if there is no separate explicit description, the numerical value or its corresponding information is not indicated by various factors (eg, process factors, internal or external shocks, noise, etc.) may be interpreted as including an error range that may occur.

Hereinafter, various embodiments of the present disclosure will be described in detail with reference to the accompanying drawings.

1 is a view showing an integrated composite reduction device 1000 according to embodiments of the present disclosure.

Referring to FIG. 1, it is possible to provide an integrated composite reduction device 1000 including a gas supply unit 1100, an inlet 1200, a reduction cartridge 1300, an outlet 1400 and a gas discharge unit 1500.

The gas supply unit 1100 is a part through which gas is supplied into the integrated composite reduction device 1000, and the inlet 1200 is a part through which the gas supplied through the gas supply unit 1100 flows into the reduction cartridge 1300.

The reduction cartridge 1300 is located between the inlet 1200 and the outlet 1400, and includes a first reduction module 1310 including hydrophilic nanoparticles and a second reduction module 1320 including hydrophobic nanoparticles.

The first reduction module 1310 functions to reduce moisture and hydrophilic VOCs in the supplied gas, and the second reduction module 1320 functions to reduce hydrophobic VOCs in the supplied gas. The outlet 1400 is a part through which gas purified through the first reduction module 1310 and the second reduction module 1320 is discharged from the reduction cartridge 1300, and the gas discharge unit 1500 is integrated with the purified gas. This is the part discharged out of the reduction device 1000.

Figure 2 is a view showing an integrated composite reduction device 1000 according to another embodiment of the present disclosure.

Referring to Figure 2, it is possible to provide an integrated composite reduction device 1000 further comprising a filter 1600 and a vacuum line 1325. The gas supplied into the integrated composite reduction device 1000 through the gas supply unit 1100 is introduced into the reduction cartridge 1300 through the filter 1600. The filter 1600 may serve to remove fine dust included in the supplied gas.

The filter 1600 may be located in the gas supply unit 1100 or the inlet 1200 . As long as the filter (1600) is located within the path through which the gas supplied to the gas supply unit 1100 flows into the reduction cartridge 1300, the location of the filter 1600 is not particularly limited.

The vacuum line 1325 includes a first vacuum line 1330 and a second vacuum line 1340, and the first vacuum line 1330 and the second vacuum line 1340 are located in the reduction cartridge 1300.

The first vacuum line 1330 is a part through which moisture and hydrophilic VOC separated from the first reduction module 1310 are discharged. The second vacuum line 1340 is a part through which the hydrophobic VOC separated from the second reduction module 1320 is discharged.

3 is a diagram showing a reduction cartridge 1300 and a vacuum line 1325 according to embodiments of the present disclosure. 4 is a view showing the first reduction module 1310 of FIG. 3, and FIG. 8 is a view showing the second reduction module 1320 of FIG.

Referring to FIG. 3 , the first vacuum line 1330 is connected to the first reduction module 1310 and the second vacuum line 1340 is connected to the second reduction module 1320 . Since the first vacuum line 1330 and the second vacuum line 1340 are connected to the first reduction module 1310 and the second reduction module 1320, respectively, water and hydrophilic VOCs and hydrophobic VOCs are separately separated and recovered. can do.

As shown in FIG. 3, the reduction cartridge 1300 may include a plurality of first reduction modules 1310 and a plurality of second reduction modules 1320. Within the abatement cartridge 1300, the arrangement and ratio of the first abatement module 1310 and the second abatement module 1320 are the field to which the abatement cartridge 1300 is applied or the hydrophilic VOC and hydrophobic VOC contained in the supplied gas. It can be adjusted and applied according to the amount of discharge. For example, in the arrangement of the first reduction module 1310 and the second reduction module 1320, a plurality of first reduction modules 1310 are located adjacent to the inlet 1200 and a plurality of second reduction modules 1320 It may be arranged adjacent to the outlet 1400, a plurality of first reduction modules 1310 are located adjacent to the outlet 1400 and a plurality of second reduction modules 1320 are located adjacent to the inlet 1200 It may be an arrangement that In addition, a plurality of first reduction modules 1310 and a plurality of second reduction modules 1320 may be arranged alternately.

In embodiments of the present disclosure, for example, in the reduction cartridge 1300, a plurality of first reduction modules 1310 are located adjacent to the inlet 1200 and a plurality of second reduction modules 1320 are disposed adjacent to the outlet 1400. ) may have an arrangement located adjacent to. When the reduction cartridge 1300 has the above arrangement, water and hydrophilic VOCs are first reduced in the first reduction module 1310 and hydrophobic VOCs are reduced in the second reduction module 1320, thereby exhibiting excellent water and VOC reduction efficiency. there is.

4, the first reduction module 1310 includes a first separator 1311, an upper header 1312 connected to the upper part of the first separator 1311, and a lower header connected to the lower part of the first separator 1311 ( 1313).

The moisture and hydrophilic VOCs separated in the first reduction module 1310 are stored in the upper header 1312 or lower header 1313, and the first vacuum line 1330 connected to the upper header 1312 or lower header 1313 It can be discharged out of the reduction cartridge 1300 through.

Here, the first vacuum line 1330 may be located in a form connected to the upper header 1312 or the lower header 1313 of the plurality of first reduction modules 1310. For example, the first vacuum line 1330 may be positioned in a form connected to the left or right side of the plurality of upper headers 1312, and may be positioned in a form connected to the left or right side of the plurality of lower headers 1313. In addition, the first vacuum line 1330 may be located in a form connected to both side surfaces of the plurality of upper headers 1312 and the plurality of lower headers 1313 . In the embodiments of the present disclosure, as long as the first vacuum line 1330 is located in a form connected to the upper header 1312 or the lower header 1313, the number and position of the first vacuum line 1330 not particularly limited

The contents of the first reduction module 1310 and the first vacuum line 1330 including the upper header 1312 and the lower header 1313 described with reference to FIGS. 3 and 4 are shown in FIGS. 3 and 8 It is the same as the description of the second reduction module 1320 and the second vacuum line 1340 including the upper header 1322 and the lower header 1323, and the first separator included in the first reduction module 1310. There is a difference only in the second separation membrane 1321 included in (1311) and the second reduction module 1320. Therefore, the first separator 1311 will be described in the description of FIGS. 5 to 7 , and the second separator 1321 will be described in the description of FIGS. 9 and 10 .

FIG. 5 is a view showing an example of the first separator 1311 of FIG. 4 , and FIG. 6 is a view showing a partial cross-section of the first separator 1311 of FIG. 5 .

5 and 6, the first separator 1311 includes a first porous support 1311A; and a first coating layer 1311B including hydrophilic nanoparticles 1311Ba and positioned on the surface of the first porous support 1311A.

Moisture and hydrophilic VOC adsorbed on the surface of the first coating layer 1311B diffuse through the first coating layer 1311B and are desorbed into the first porous support 1311A. The first separation membrane 1311 may exhibit moisture and hydrophilic VOC reduction effects through the above process.

The first coating layer 1311B is positioned on the surface of the first porous support 1311A. The first porous support 1311A may serve to mechanically support the first coating layer 1311B.

The first porous support 1311A may be selected according to the shape of the first separator 1311. The first porous support 1311A may be a separator having a shape selected from the group consisting of a hollow fiber type, a flat plate type, a tubular type, and a spiral wound type. For example, the first porous support 1311A may be a hollow fiber separator.

In addition, the first porous support 1311A may be selected according to the material of the first separator 1311. The first porous support 1311A is made of polysulfone, polyethersulfone, sulfonated polysulfone, polyvinylidene fluoride, polyacrylonitrile, polyimide, polyetherimide, polyester, polybenzimidazole and polyamide. It may contain one or more selected from the group. For example, the first porous support 1311A may include polysulfone.

In embodiments of the present disclosure, the first porous support 1311A may be, for example, a hollow fiber separator containing polysulfone, but the first porous support 1311A is not limited thereto.

The first coating layer 1311B includes hydrophilic nanoparticles 1311Ba and is positioned on the surface of the first porous support 1311A. Since the first coating layer 1311B selectively reacts with moisture and hydrophilic VOCs, it may be referred to as a selective coating layer or a selective layer.

The first coating layer 1311B may include a polymer matrix synthesized by polymerizing a water-soluble monomer and an organic monomer and hydrophilic nanoparticles 1311Ba. For example, the first coating layer 1311B is an interface between diethylene triamine (hereinafter referred to as "DETA"), which is a water-soluble monomer, and trimesoyl chloride (hereinafter referred to as "TMC", which is an organic monomer). It may include a polymer matrix synthesized by polymerization and Engelhard Titanosilicate-4 (ETS-4) nanoparticles.

For example, when a solution containing DETA and ETS-4 nanoparticles and a solution containing TMC are polymerized at the interface between the solutions, the ETS-4 nanoparticles are dispersed in the polymer matrix to form the first coating layer 1311B. can form

The ETS-4 nanoparticles are chemically resistant to VOCs, microporous and hydrophilic.

Since the ETS-4 nanoparticles are composed of only Ti, Si, and O elements, which are inorganic materials having excellent chemical resistance to VOC, the first coating layer 1311B including the ETS-4 nanoparticles has excellent chemical resistance to VOC. can

In addition, the pores of ETS-4 nanoparticles are about 4 Å, but the size of water molecules is 2.65 Å and the size of toluene molecules, which is a hydrophobic VOC, is 5.85 Å, which is larger than the pores of ETS-4 nanoparticles. The included first coating layer 1311B may serve to selectively transmit moisture due to a pore size exclusion effect.

In addition, since ETS-4 nanoparticles are known as hydrophilic materials, the first coating layer 1311B including ETS-4 nanoparticles may exhibit excellent effects in separating moisture and hydrophilic VOCs.

FIG. 7 is a partial cross-sectional view of another example of the first separator 1311 of FIG. 5 .

Referring to FIG. 7 , the first separator 1311 may further include a second coating layer 1311C. The second coating layer 1311C may be positioned between the first porous support 1311A and the first coating layer 1311B. In the process of forming the first coating layer 1311B on the first porous support 1311A, the second coating layer 1311C reacts with the coating solution used for coating the first coating layer 1311B to form the first coating layer 1311B. It may serve to facilitate coating on the first porous support 1311A.

The second coating layer 1311C may include a material reactive with a hydrophilic material (hereinafter referred to as a “reactive agent”). As the reactive agent for the hydrophilic material, a cross-linking agent, a coagulant, and a reaction modifier for the hydrophilic material may be used. The reactive agent of the hydrophilic material may be selected from the group consisting of, for example, calcium chloride, aluminum nitrate, aluminum sulfate, copper sulfate, hydrochloric acid, sulfuric acid and glutaraldehyde.

For example, in the process of coating the first coating layer 1311B containing ETS-4 nanoparticles on the first porous support 1311A containing hydrophobic polysulfone, the first coating layer 1311B containing a hydrophilic reactant The second coating layer 1311C may be positioned on the surface of the first porous support 1311A to facilitate coating of the first coating layer 1311B.

FIG. 9 is a view showing the second separator 1321 of FIG. 8 , and FIG. 10 is a partial cross-sectional view of an example of the second separator 1321 of FIG. 9 .

9 and 10, the second separator 1321 includes a second porous support 1321A; and a third coating layer 1321B including hydrophobic nanoparticles 1321Ba and positioned on the surface of the second porous support 1321A.

The hydrophobic VOC adsorbed on the surface of the third coating layer 1321B diffuses through the third coating layer 1321B and is desorbed into the second porous support 1321A. The second separator 1321 may exhibit a hydrophobic VOC reduction effect through the above process.

The second porous support 1321A may be selected according to the shape of the second separator 1321 . The second porous support 1321A may be a separator having a shape selected from the group consisting of a hollow fiber shape, a flat plate shape, a tubular shape, and a spiral wound shape. For example, the second porous support 1321A may be a hollow fiber separator.

In addition, the second porous support 1321A may be selected according to the material of the second separator 1321. The second porous support 1321A may include one or more selected from the group consisting of fluorine-based polymers, sulfone-based polymers, and olefin-based polymers. For example, the second porous support 1321A may include polyvinylidene fluoride, which is a fluorine-based polymer.

In embodiments of the present disclosure, for example, the second porous support 1321A may be a hollow fiber separator containing polyvinylidene fluoride, but the second porous support 1321A is not limited thereto.

The polyvinylidene fluoride polymer exhibits high mechanical strength, thermal stability and excellent chemical resistance compared to other polymers. In particular, polyvinylidene fluoride is a polymer having chemical resistance to organic contaminants such as VOC.

In order to coat the surface of the second porous support 1321A with the third coating layer 1321B, a coating solution containing a hydrophobic rubbery polymer may be used. As the hydrophobic rubbery polymer, a rubbery polymer having high gas permeability and easy coating may be used. The third coating layer 1321B including the hydrophobic rubbery polymer has a high affinity for VOCs and has a high free volume, so it can play a role of facilitating the diffusion of VOCs. The hydrophobic rubbery polymer may be selected from the group consisting of polyether block amide (PEBA), ethylene vinyl acetate (EVA) and siloxane-based polymers. For example, the hydrophobic rubbery polymer included in the third coating layer 1321B may be polydimethylsiloxane (PDMS), which is a siloxane-based polymer.

The third coating layer 1321B may include hydrophobic nanoparticles 1321Ba to improve hydrophobic VOC reduction efficiency. As the hydrophobic nanoparticles 1321Ba, hydrophobic nanoparticles having a large specific surface area and a very small pore size may be used. For example, the third coating layer 1321B may include tungsten trioxide (WO ₃ ) nanoparticles.

FIG. 11 is a view showing a coating step of the separator 2301 according to embodiments of the present disclosure, and FIG. 12 is a view showing the structure of the separator 2301 manufactured according to FIG. 11 .

Referring to FIG. 11, after pre-treatment of the porous support 2301A, it is impregnated into a coating solution in which nanoparticles 2301Ba are dispersed. Thereafter, the separator 2301 is manufactured by forming a coating layer 2301B on the surface of the porous support 2301A through heat treatment.

The pretreatment of the porous support (2301A) means a process for the purpose of protecting the membrane and controlling fouling. Here, fouling is a phenomenon in which clogging or the formation of an adhesive layer is caused as solutes in raw water are blocked by the membrane, which reduces the filtering function of the membrane. As a pretreatment process, a screen to remove impurities, a pre-filter or strainer, etc., injection of coagulant to improve filtration performance, or injection of chlorine agent to prevent adhesion of organic matter to algae, membranes, and oxidation of iron, manganese, etc. It is known that there is fairness.

The separator 2301 made by the coating step includes a porous support 2301A and a coating layer 2301B located on the surface of the porous support 2301A. In embodiments of the present disclosure, the coating layer 2301B may be a coating layer including a first coating layer 1311B or a third coating layer 1321B or a first coating layer 1311B and a second coating layer 1311C.

The nanoparticle 2301Ba is defined as a particle having a size of 1 nm to 100 nm in at least one dimension. The nanoparticles 2301Ba may be selected from the group consisting of quantum dots, metal nanoparticles, magnetic nanoparticles, and carbon nanotubes. In embodiments of the present disclosure, the nanoparticle 2301Ba may be a transition metal nanoparticle. For example, the nanoparticles included in the first separator 1311 and the second separator 1321 may be titanium (Ti) nanoparticles and tungsten (W) nanoparticles, respectively.

The nanoparticles 2301Ba may have a functional group located on the surface of the core particle. In organic chemistry, the functional group is defined as a specific substituent or moiety in a molecule responsible for a chemical reaction characteristic of molecules. The functional group that binds to the central atom in a coordination compound is called a ligand. In embodiments of the present disclosure, the functional group may be a ligand located on the surface of the transition metal nanoparticle. For example, the nanoparticles 2301Ba including the ligand on the surface may be included in the coating layer 2021B in a dispersed form in a polymer matrix and positioned on the surface of the porous support 2301A.

According to other embodiments of the present disclosure, it is possible to provide a composite reduction method using the integrated composite reduction device (1000). The gas supply step is a step in which gas is supplied to the gas supply unit 1100 . The first reduction step is a step in which moisture and hydrophilic VOC of the supplied gas are reduced. The second reduction step is a step in which hydrophobic VOCs in the supplied gas are reduced. The gas discharge step is a step in which the gas purified through the first reduction step and the second reduction step is discharged to the gas discharge unit 1500 .

The first reduction step may be a step in which the relative humidity of the supplied gas is reduced to 50% or less. For example, it may be a step in which supplied gas having a relative humidity of 70% is reduced to 50% or less through the first reduction module 1310 including ETS-4 nanoparticles.

The second reduction step may be a step in which the hydrophobic VOC of the supplied gas is reduced by 60% to 90%. For example, the hydrophobic VOC contained in the gas supplied through the second reduction module 1320 including WO ₃ nanoparticles may be reduced by 60% to 90%.

Hereinafter, experimental examples according to the present disclosure according to the above configuration will be described.

Experimental Example 1. Long-term durability evaluation of the first reduction module 1310

An experiment was conducted to evaluate the durability of the first reduction module 1310 including the first separator 1311 containing ETS-4 nanoparticles. After flowing a mixed gas of 400 ppm of toluene with nitrogen through the first reduction module 1310 for one month, the permeability of the first reduction module 1310 is measured and compared with the moisture permeability value before long-term durability evaluation. The first reduction module ( 1310) was evaluated for long-term durability. The first separator 1311 prepared for evaluation is a coating solution in which 0.2 wt% of ETS-4 nanoparticles are added relative to the weight of DETA on the first porous support 1311A, which is a polysulfone hollow fiber membrane, and the first coating layer 1311B It was prepared by coating. The results of long-term durability evaluation are as follows.

The first reduction module 1310 before long-term durability evaluation showed an average transmittance of 1428 GPU at a relative humidity of 20% to 80%, and showed a transmittance of 1578 GPU at a reference relative humidity of 70%.

Thereafter, a mixed gas in which 400 ppm of toluene was mixed with nitrogen was flowed at a flow rate of 20 ml/min for one month, and then the permeability was measured again.

At 20% to 80% relative humidity, the average permeability was 1435 GPU, 7 GPU increased rather than before long-term durability evaluation, and at 70%, the standard relative humidity, 1565 GPU, 13 GPU (about 13%) decreased than before evaluation. As a result, it can be determined that the first reduction module 1310 of Experimental Example 1 has excellent long-term durability against VOCs including toluene.

In addition, the selectivity of the first reduction module 1310 was measured in the same way. The first reduction module 1310 before long-term durability evaluation showed an average selectivity of 357 at a relative humidity of 20% to 80%, and a selectivity of 479 at a standard relative humidity of 70%.

The first reduction module 1310 after long-term reconstitution evaluation showed an average selectivity of 278 at a relative humidity of 20% to 80%, and a selectivity of 379 at a reference relative humidity of 70%.

Similar to the transmittance, it can be determined that the first reduction module 1310 of Experimental Example 1 has excellent long-term durability against VOCs containing toluene.

Experimental Example 2. Evaluation of reduction efficiency of the second reduction module 1320.

The second separator 1321 was prepared by coating the third coating layer 1321B containing PDMS and WO ₃ nanoparticles on the surface of the second porous support 1321A, which is a PVDF hollow fiber membrane, and the second separator 1321 was formed. 2 The toluene removal efficiency of the reduction module 1320 was measured. For the measurement, a mixed gas in which 400 ppm of toluene was mixed with nitrogen was used, and the measurement results are as follows.

As the content of PDMS increased, it was confirmed that the concentration of permeated toluene decreased, indicating that the toluene removal efficiency was improved. The second reduction module 1320 containing 20wt% PDMS showed a removal efficiency of 76.0%, and the second reduction module 1320 further including 0.1wt% WO ₃ nanoparticles had a removal efficiency of 80.1%. showed The inclusion of WO ₃ nanoparticles in the second reduction module 1320 showed an effect of improving efficiency by 4.1%. The toluene removal efficiency of up to 87.9% was shown in the second reduction module 1320 containing 25wt% PDMS. As a result, it can be determined that the second reduction module 1320 of Experimental Example 2 exhibits excellent toluene removal efficiency.

Experimental examples according to the above-described configuration have been described, but the same effect can be obtained even if the first reduction module 1310 and the second reduction module 1320 are replaced with other components or materials described above.

According to embodiments of the present disclosure, by using hydrophilic nanoparticles and hydrophobic nanoparticles, it is possible to provide an integrated composite reduction device having excellent chemical resistance to VOC.

According to embodiments of the present disclosure, since water and hydrophilic VOCs and hydrophobic VOCs are reduced at the same time, it is possible to efficiently utilize space and provide an integrated composite reduction device capable of reducing costs accordingly.

According to embodiments of the present disclosure, by using a reduction module for reducing moisture and hydrophilic VOC and a reduction module for reducing hydrophobic VOC, it is possible to provide a composite reduction method with excellent VOC reduction efficiency.

The above description is merely an example of the technical idea of the present disclosure, and various modifications and variations may be made to those skilled in the art without departing from the essential characteristics of the present disclosure. In addition, the embodiments disclosed in this disclosure are not intended to limit the technical idea of the present disclosure, but rather to explain the scope of the technical idea of the present disclosure by these embodiments. The scope of protection of the present disclosure should be construed by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of rights of the present disclosure.

1000: integrated composite reduction device 1100: gas supply unit
1200: inlet 1300: reduction cartridge
1310: first reduction module 1311: first separator
1311A: first porous support 1311B: first coating layer
1311Ba: hydrophilic nanoparticles 1311C: second coating layer
1320: second reduction module 1321: second separator
1321A: second porous support 1321B: third coating layer
1321Ba: hydrophobic nanoparticles 1325: vacuum line
1330: first vacuum line 1340: second vacuum line
1400: outlet 1500: gas outlet
1600: filter

Claims (14)

inlet;
A reduction cartridge including a first reduction module including hydrophilic nanoparticles and a second reduction module including hydrophobic nanoparticles; and
All-in-one combined reduction device including an outlet. According to claim 1,
A gas supply unit connected to the inlet and
Integrated composite reduction device further comprising a filter located in the gas supply unit or the inlet. According to claim 1,
A first vacuum line connected to the first reduction module and
An integrated composite reduction device further comprising a second vacuum line connected to the second reduction module. According to claim 1,
The first reduction module is located adjacent to the inlet, and the second reduction module is an integrated composite reduction device located adjacent to the outlet. According to claim 1,
The first reduction module is an integrated composite reduction device including a first separator including a first porous support and a first coating layer including the hydrophilic nanoparticles. According to claim 5,
The first separator is an integrated composite reduction device further comprising a second coating layer located between the first porous support and the first coating layer. According to claim 5,
Wherein the first porous support is a hollow fiber membrane containing a sulfone-based polymer integrated composite reduction device. According to claim 1,
The hydrophilic nanoparticles are ETS-4 (Engelhard Titanosilicate-4) nanoparticles integrated composite reduction device. According to claim 1,
The second reduction module is an integrated composite reduction device including a second separator including a second porous support and a third coating layer including the hydrophobic nanoparticles. According to claim 9,
The second porous support is an integrated composite reduction device of a hollow fiber membrane containing a fluorine-based polymer. According to claim 1,
The hydrophobic nanoparticles are tungsten trioxide (WO ₃ ) nanoparticles integrated composite reduction device. a gas supply step in which gas is supplied to the gas supply unit;
A first reduction step in which moisture and hydrophilic VOC of the supplied gas are reduced;
a second reduction step in which hydrophobic VOCs in the supplied gas are reduced; and
A complex reduction method comprising a gas discharge step in which the gas purified through the first reduction step and the second reduction step is discharged from a gas discharge unit. According to claim 12,
The first reduction step is a step of reducing the relative humidity of the supplied gas to 50% or less. According to claim 12,
The second reduction step is a complex reduction method in which the hydrophobic VOC of the supplied gas is reduced by 60% to 90%.

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