KR20230061253A - Continuous manufacturing apparatus and continuous manufacturing method of metal-organic framework(mof) - Google Patents

Abstract

The present invention relates to a continuous production apparatus and continuous production method of a metal organic framework. According to the present invention, it is possible to provide a manufacturing apparatus and manufacturing method capable of mass-producing a metal organic framework having excellent gas adsorption performance through a continuous process.

Description

CONTINUOUS MANUFACTURING APPARATUS AND CONTINUOUS MANUFACTURING METHOD OF METAL-ORGANIC FRAMEWORK (MOF)

The present invention relates to a continuous manufacturing apparatus and method for producing a metal organic framework (MOF), and more particularly, to a manufacturing apparatus and manufacturing method capable of mass-producing a metal organic framework having excellent gas adsorption performance through a continuous process. will be. This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0145501 filed on October 28, 2021, and all contents disclosed in the Korean Patent Application Document are included as part of this specification.

Metal-organic frameworks (MOFs) are a class of promising porous materials with functionalities, relatively large pore sizes, and high levels of surface area. The aforementioned features enable numerous industrial applications such as gas storage, gas separation, adsorption, drug delivery and catalysis. However, until now, the cost of these materials is still very high, making their practical use difficult, and thus, the commercial use of metal organic frameworks has been limited. Only very few metal-organic frameworks described in the academic literature are commercially available, and it can be seen that such availability is also limited to a small amount.

An important requirement for approaching commercial applications of metal-organic frameworks is the ability to routinely synthesize large quantities (kg scale or larger) of metal-organic framework materials at economical cost. In order to apply these materials in practice, the manufacturing process should be an efficient and scalable synthesis process capable of producing large amounts of metal organic frameworks.

However, traditional laboratory routes, such as typical solvothermal synthesis, are difficult to scale-up due to extended reaction times (about 24 hours) and low material yields.

In this regard, continuous flow chemistry can be considered a useful tool. Improved available heat and mass transfer can often result in improved reaction yields, reduced reaction times, and faster reaction synthesis. Considering the large number of known metal-organic frameworks and the vast number of possible applications, each of which requires a different metal-organic framework in the future, there is a market demand for manufacturing equipment and process-related technologies that can be widely applied. Accordingly, there is a need to provide new or improved devices and methods for preparing metal organic frameworks.

Capability of CO2 on Metal-Organic Frameworks-Based Porous Adsorbents and Their Challenges to Pressure Swing Adsorption Applications (Clean Technology Volume 19, Issue4, p370~378, 31 Dec 2013)

An object of the present invention is to provide a manufacturing apparatus and manufacturing method capable of mass-producing a metal organic framework having excellent gas adsorption performance through a continuous process.

The technical problem to be achieved by the present invention is not limited to the above-mentioned technical problem, and other technical problems not mentioned can be clearly understood by those skilled in the art from the description below. There will be.

In order to achieve the above technical problem, one aspect of the present invention,

As a manufacturing device of a metal organic framework (Metal Organic Framework),

first and second precursor storage units;

a reaction unit synthesizing a metal organic framework by mixing the first and second precursors;

a first transfer unit transferring the precursor from the first precursor storage unit to the reaction unit; and a second transfer unit transferring the precursor from the second precursor storage unit to the reaction unit. and

a filtering unit filtering the metal organic framework synthesized in the reaction unit; including,

The manufacturing apparatus provides a manufacturing apparatus for a metal-organic skeleton, characterized in that it consists of a continuous process.

Another aspect of the present invention is,

As a method for producing a metal organic framework,

Injecting the first and second precursors into the first and second precursor storage units, respectively;

transferring the first and second precursors to a reaction unit;

synthesizing a metal organic framework by mixing the first and second precursors in the reaction unit; and

filtering the synthesized metal organic framework; including,

The manufacturing method provides a method for preparing a metal-organic framework, characterized in that it consists of a continuous process.

According to the present invention, a manufacturing apparatus and manufacturing method capable of mass-producing a metal organic framework having excellent gas adsorption performance through a continuous process can be provided. In addition, according to the present invention, rapid crystallization of the metal organic framework is possible through efficient mixing of the reactant flow, the reaction rate can be controlled by precisely controlling the reaction temperature and residence time, and the production scale can be expanded with a modular process configuration. This is possible, and it is also advantageous for production scale expansion by synthesizing the metal organic framework at room temperature and lowering energy consumption.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the description of the present invention or the configuration of the invention described in the claims.

1 is a schematic diagram showing an embodiment of a manufacturing apparatus for a metal-organic framework of the present application.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in many different forms and, therefore, is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, combined)" with another part, this is not only "directly connected", but also "indirectly connected" with another member in between. "Including cases where In addition, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

Terms used in this specification are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

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

The first aspect of the present invention is,

An apparatus for manufacturing a metal organic framework, comprising: first and second precursor storage units; a reaction unit synthesizing a metal organic framework by mixing the first and second precursors; a first transfer unit transferring the precursor from the first precursor storage unit to the reaction unit; and a second transfer unit transferring the precursor from the second precursor storage unit to the reaction unit. and a filtering unit filtering the metal organic framework synthesized in the reaction unit. Including, the manufacturing apparatus provides a manufacturing apparatus for a metal organic framework, characterized in that consisting of a continuous process.

Hereinafter, an apparatus for manufacturing a metal organic framework according to a first aspect of the present invention will be described in detail.

In one embodiment of the present invention, the metal organic framework manufacturing apparatus of the present application may include first and second precursor storage units 11 and 12 . The first and second precursor storage units may store first and second precursors, respectively. Each of the first and second precursors may be a metal precursor or an organic ligand described later.

In one embodiment of the present invention, the first precursor storage unit 11 or the second precursor storage unit 12 is a means capable of storing a liquid mixture such as a drum, separator, vessel, tank, etc. without limitation. may be available

In one embodiment of the present invention, the metal organic framework manufacturing apparatus of the present application includes a first transfer unit 31 for transferring a precursor from the first precursor storage unit 11 to the reaction unit 20 and the second precursor storage unit A second transfer unit 32 for transferring the precursor from the unit 12 to the reaction unit 20 may be included. The first transfer unit 31 or the second transfer unit 32 may refer to a means capable of transferring a metal precursor or an organic ligand in a solution state, preferably a pump, more preferably a metering supply pump. . When the first or second transfer units 31 and 32 are pumps, they are mixed in advance through a joining member such as a T-piece type mixer, a Y-type mixer, or a cross junction mixer at the front end of the reaction unit 20 to react It may be conveyed to section 20, or it may be conveyed to reaction section 20 without prior mixing.

In one embodiment of the present invention, the mixing supply ratio of the second precursor to the first precursor in the reaction unit 20 based on weight may be 0.1 to 50. In another embodiment, the mixing supply ratio by weight of the second precursor to the first precursor in the reaction unit 20 is 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, or 0.6 or more, or 45 or less, or 40 or less. , 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, but is not limited thereto, and may be adjusted according to the type of metal organic framework desired, the type of precursor, etc.

In one embodiment of the present invention, the mixed supply ratio of the second precursor to the first precursor in the reaction unit 20 may be controlled by a metered feed pump.

In one embodiment of the present invention, the manufacturing apparatus of the metal organic framework of the present application may include a reaction unit 20 for synthesizing the metal organic framework by mixing the first precursor and the second precursor. The number of reaction units 20 may be plural according to the needs of a continuous process, or the volume of the reaction unit 20 may be set to a volume sufficient to accommodate the precursors for a sufficient time to synthesize the metal organic framework. .

In one embodiment of the present invention, the volume of the reaction unit 20 is 0.001 m ³ to 0.05 m ³ It may be characterized in that. In another embodiment, the volume of the reaction unit 20 is 0.002 m ³ or more, 0.003 m ³ or more, or 0.004 m ³ or more, or 0.045 m ³ or less, 0.04 m ³ or less, 0.035 m ^{3 or} less, or 0.03 m ³ or less, 0.025 m ³ or less, 0.02 m ³ or less, 0.015 m ^{3 or} less, or 0.01 m ^{3 or} less.

In one embodiment of the present invention, the residence time for synthesizing the metal organic framework in the reaction unit 20 may be characterized in that it is 0.1 to 6 hours. In the present specification, the term “residence time” may refer to a residence time in the reaction unit 20 from immediately after the precursors, for example, the first and second precursors are put into the reaction unit 20 . In this specification, the term "maximum residence time" may mean the maximum time that both the first and second precursors can stay in the reaction unit 20 from immediately after being introduced into the reaction unit 20, which is the reaction unit ( 20) can be proportional to its volume. In another embodiment, the residence time for synthesizing the metal organic framework in the reaction unit 20 is 0.2 hours or more, 0.3 hours or more, 0.4 hours or more, 0.5 hours or more, 0.6 hours or more, 0.7 hours or more, or 0.8 hours or more. or more than 0.9 hours, or less than 5 hours, less than 4 hours, less than 3 hours or less than 2 hours. The retention time may be appropriately controlled according to the type of metal organic framework to be prepared.

In one embodiment of the present invention, the residence time for metal-organic framework synthesis in the reaction unit 20 may be characterized in that it is controlled by an automatic valve or manually. When the retention time is controlled using an automatic valve, the metal organic framework synthesized in the reaction unit 20 may be automatically delivered to the filtering unit 30 when the preset retention time elapses.

In one embodiment of the present invention, the operating temperature of the reaction unit 20 may be characterized in that 10 ℃ to 100 ℃. In another embodiment, the operating temperature of the reaction part 20 is 15 ℃ or more, 20 ℃ or more, or 25 ℃ or more, 90 ℃ or less, 80 ℃ or less, 70 ℃ or less, 60 ℃ or less, 50 ℃ or less , It may be 40 ℃ or less or 30 ℃ or less, but is not limited thereto, and the operating temperature of the reaction unit 20 depends on the reaction chemistry and desired reaction kinetics in the formation of the metal organic framework to be prepared. can be different. By satisfying the above-described range, the temperature may be adjusted to the most appropriate temperature range in preparing the metal-organic frameworks of the present invention, and thus the production scale may be expanded.

In one embodiment of the present invention, the operating temperature of the reaction unit 20 may be characterized in that it is controlled by a fully automatic control device.

In one embodiment of the present invention, the operating pressure of the reaction unit 20 may be characterized in that -1 to 5 bar. In another embodiment, the operating pressure of the reaction unit 20 is -0.5 bar or more, 0 bar or more, or 0.5 bar or more, or 4.5 bar or less, 4 bar or less, 3.5 bar or less, 3 bar or less, 2.5 bar or less, It may be 2 bar or less or 1.5 bar or less, but is not limited thereto, and may vary depending on the metal organic framework to be prepared. By satisfying the above-described range, the pressure may be adjusted to the most appropriate pressure range, particularly in preparing the metal-organic frameworks of the present invention.

In one embodiment of the present invention, the operating pressure of the reaction unit 20 may be characterized in that it is controlled by a fully automatic control device.

In one embodiment of the present invention, the first precursor is 1 selected from the group consisting of zinc nitrate hexahydrate, iron nitrate nonahydrate, zinc oxide, and combinations thereof. It can be characterized as being a metal precursor of more than one species. Preferably, when the metal organic framework to be prepared is ZIF-8, the metal precursor may be zinc nitrate hexahydrate, and when the metal organic framework to be prepared is Fe-BTC, the metal precursor may be iron nitrate nonhydrate. can

In one embodiment of the present invention, the second precursor is at least one organic ligand selected from the group consisting of 2-methylimidazole, trimesic acid, and combinations thereof. can be done with Preferably, when the metal organic framework to be prepared is ZIF-8, the organic ligand may be 2-methylimidazole, and when the metal organic framework to be prepared is Fe-BTC, the organic ligand may be trimesic acid. there is. In this specification, the terms “first and second precursors” or “first and second precursor storage units” are not concepts indicating an order, and are used to distinguish different types of precursors or storage units for storing different types of precursors. It is a concept.

In one embodiment of the present invention, a pH adjusting agent may be further added to the second precursor storage unit 12 . Triethanolamine may be exemplified as the pH adjusting agent, but is not limited thereto, and any known pH adjusting agent may be used without limitation as long as the object of the present invention is not impaired.

In one embodiment of the present invention, the metal-organic framework manufacturing apparatus of the present application may include a filtering unit 40 for filtering the metal-organic framework synthesized in the reaction unit 20 . The pore size of the filter of the filtration unit 40 may be characterized in that 0.1 to 5 ㎛. In another embodiment, the pore size of the filter of the filtering unit 40 is 0.5 μm or more, 1 μm or more, 1.5 μm or more, 2 μm or more, or 2.5 μm or more, or 4.5 μm or less, 4 μm or less, or 3.5 μm may be below. By satisfying the above range, the prepared metal organic framework particles can be properly separated from impurities.

In one embodiment of the present invention, the filter of the filtering unit 40 may be characterized in that it is a replaceable filter. The replacement cycle can be appropriately set in consideration of the scale of the process.

In one embodiment of the present invention, the manufacturing apparatus of the metal-organic framework of the present application is characterized in that it further comprises a drying unit (not shown) for drying and powdering the metal-organic framework filtered by the filtering unit 40. can be done with In the case of the drying process, for removing the solvent remaining in the metal organic framework particles, various drying processes used in the art may be used without limitation.

In one embodiment of the present invention, the metal-organic framework manufacturing apparatus of the present application may further include an ultrasonic separation device (not shown). The ultrasonic separation device may remove contaminants from pores by purifying the metal-organic framework, and improve the surface area of the metal-organic framework to provide a metal-organic framework with a large surface area.

In one embodiment of the present invention, the metal-organic framework manufacturing apparatus of the present application may be characterized in that it has a modular process configuration. In this specification, the term “modular process” refers to components constituting a manufacturing apparatus (eg, precursor storage units 11 and 12, reaction units 20, transfer units 31 and 32, filtering units 40, etc. ) may mean a device that can be independently introduced as one module. The apparatus for manufacturing a metal-organic framework of the present application may be formed by combining appropriate constituent parts according to the purpose.

In one embodiment of the present invention, the metal-organic framework manufacturing apparatus of the present application may be characterized in that it produces the metal-organic framework at a rate of 0.01 to 0.5 kg/h. In another embodiment, the speed is greater than or equal to 0.015 kg/h, less than or equal to 0.4 kg/h, less than or equal to 0.3 kg/h, less than or equal to 0.2 kg/h, less than or equal to 0.1 kg/h, less than or equal to 0.09 kg/h, or less than or equal to 0.08 kg/h. h or less, 0.07 kg/h or less, or 0.06 kg/h or less.

In one embodiment of the present invention, the metal organic framework manufacturing apparatus of the present application may be characterized in that it has a yield of 95%. In this specification, the term “yield” may refer to a % ratio of the yield of the metal organic framework to the total amount of the first precursor and the second precursor. In another embodiment, the yield is 96% or more, 97% or more, 98% or more, 99% or more, 100% or more, 101% or more, 102% or more, 103% or more, 104% or more, 105% or more, 106% or more, 107% or more, 108% or more, 109% or more, 110% or more, 111% or more, 112% or more, 113% or more, 114% or more, 115% or more, 116% or more, 117% or more, 118% 119% or more, 120% or more, 121% or more, 122% or more, 123% or more, 124% or more, or 125% or more, or 150% or less, 140% or less, 130% or less, 120% or less, 110% or less or less than 100%.

In one embodiment of the present invention, the manufacturing apparatus of the metal-organic framework of the present application may be characterized in that it consists of a continuous process. In the metal organic framework manufacturing apparatus of the present application, the precursor storage unit 11 and 12, the transfer unit 31 and 32, the reaction unit 20, the filtration unit 40, and/or optionally the precursor supply unit are organically linked. Therefore, it is possible to produce the desired metal organic framework with high yield and productivity, and it is possible to expand the production scale.

In one embodiment of the present invention, a plurality of apparatuses for manufacturing a metal-organic framework of the present application may be provided, and each of the plurality of manufacturing apparatuses may be characterized in that they produce different metal-organic frameworks.

A second aspect of the present invention is,

A method of manufacturing a metal organic framework, comprising: introducing first and second precursors into first and second precursor storage units, respectively; transferring the first and second precursors to a reaction unit; synthesizing a metal organic framework by mixing the first and second precursors in the reaction unit; and filtering the synthesized metal organic framework; Including, the manufacturing method provides a method for preparing a metal organic framework, characterized in that consisting of a continuous process.

Although detailed descriptions of parts overlapping with those of the first aspect of the present invention have been omitted, the description and contents of the first aspect of the present invention can be equally applied even if the description is omitted from the second aspect.

Hereinafter, the method for preparing the metal organic framework according to the second aspect of the present invention will be described in detail.

In one embodiment of the present invention, the method for preparing the metal organic framework of the present application may include introducing first and second precursors into the first and second precursor storage units 11 and 12, respectively. The input may be directly supplied periodically by manpower or may be automatically supplied from a separate raw material tank. In the case of automatic supply from the raw material tank, the precursor supply amount may be controlled based on the level or operation time of each raw material tank, but the control method may be used without limitation.

In one embodiment of the present invention, the method for preparing the metal organic framework of the present application may include transferring the first and second precursors to the reaction unit 20 .

In one embodiment of the present invention, the method for preparing the metal organic framework of the present application may include synthesizing the metal organic framework by mixing the first and second precursors in the reaction unit 20 .

In one embodiment of the present invention, the preparation method of the metal organic framework of the present application may include filtering the synthesized metal organic framework.

In one embodiment of the present invention, the preparation method of the metal organic framework of the present application may further include drying and pulverizing the filtered metal organic framework.

In one embodiment of the present invention, the preparation method of the metal-organic framework of the present application may further include an ultrasonic separation step.

The third aspect of the present invention is,

It provides a method for producing a fiber-particle composite, comprising the step of complexing the metal organic framework prepared by the above method on fibers.

Detailed descriptions of portions overlapping with the first and second aspects of the present application have been omitted, but the contents described for the first and second aspects of the present application can be equally applied even if the description is omitted in the third aspect.

Hereinafter, a method for manufacturing a fiber-particle composite according to the third aspect of the present application will be described in detail.

In one embodiment of the present invention, the step of complexing the metal organic framework on the fiber may be characterized by electrospinning by mixing the metal organic framework with a polymer solution. In this case, if a certain level of complexation is made in the electrospinning solution in advance, a fibrous phase may be formed.

In one embodiment of the present invention, the step of complexing the metal organic framework onto the fiber may be characterized in that the fiber is immersed in a solution containing the metal organic framework and padded. As described above, after forming a solution including the metal organic framework that has been subjected to the filtration process, the step of padding the fiber substrate in the solution may be performed. The padding step may mean that the fiber is immersed in a solution containing the metal organic framework for a predetermined time while being transported by a roller, and then transferred to a later step.

Through the methods described in the various embodiments of the present invention described above, it will be possible to scale-up and produce a fiber-particle composite in which a metal organic framework manufactured with high efficiency by the manufacturing apparatus of the present invention is composited on a fiber substrate. It can be used for filter products that respond to harmful gases and fine dust.

A fourth aspect of the present invention is,

Provided is a filter for gas adsorption comprising a fiber-particle composite manufactured according to the above manufacturing method.

Detailed descriptions of portions overlapping with the first to third aspects of the present application have been omitted, but the contents described for the first to third aspects of the present application can be equally applied even if the description is omitted in the fourth aspect.

Hereinafter, a gas adsorption filter according to a fourth aspect of the present disclosure will be described in detail.

In one embodiment of the present invention, the gas adsorption filter may be characterized in that it adsorbs at least one harmful gas selected from the group consisting of ammonia, hydrogen sulfide, and formaldehyde.

In one embodiment of the present invention, the gas adsorption filter may be a fine dust removal filter. In the case of the fine dust removal filter, it may be a HEPA filter, in which case it can filter fine dust and ultrafine dust and at the same time remove the above-mentioned harmful gases, which is harmful to the human body when applied for home and industrial purposes. It would have the advantage of being able to consolidate and remove the material.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Example 1.

A metal organic framework was synthesized by the following method using the manufacturing apparatus of FIG. 1 .

First, zinc nitrate hexahydrate is supplied as a metal precursor to the first precursor storage unit 11, and 2-methylimidazole is supplied as an organic ligand to the second precursor storage unit 12. supply At this time, 54.87 g (0.184 mol) of the zinc nitrate hexahydrate and 120.9 g (1.473 mol) of the 2-methylimidazole were supplied. In addition, for pH control, triethanolamine was additionally added to the second precursor storage unit 12.

Subsequently, the metal precursor is supplied to the reaction unit 20 through the first transfer unit 31 and the organic ligand is supplied to the reaction unit 20 through the second transfer unit 32 . It is characterized in that each of the first and second transfer units use a peristaltic hose pump (a metering supply pump). At this time, the weight ratio of the metal precursor and the organic ligand supplied to the reaction unit 20 was controlled to be 1:8 (metal precursor: ligand), and the volume of the reaction unit 20 was 0.005 m ³ (maximum of the metal precursor and ligand). It was made so that the retention time could be 2 hours).

After all the metal precursors and ligands were supplied to the reaction unit 20, the reaction was performed for 1 hour (residence time) under conditions of room temperature and 1 bar.

The metal organic framework generated in the reaction section was transferred through a filtering section 40 equipped with a filter having a pore size of 3 microns, and then naturally dried.

As a result, a powdered metal organic framework (ZIF-8) was obtained.

The yield of the metal organic framework prepared by the above-described apparatus was about 0.05 kg per hour, and the yield relative to the total amount of the metal precursor and the ligand was about 126%. This is an excellent level when considering the commonly known continuous process production and yield of ZIF-8.

Example 2.

A metal organic framework was synthesized by the following method using the manufacturing apparatus of FIG. 1 .

First, iron nitrate nonahydrate is supplied to the first precursor storage unit 11 as a metal precursor, and trimesic acid is supplied to the second precursor storage unit 12 as a ligand. At this time, the iron nitrate nonhydrate was supplied in an amount of 34.3 g (0.085 mol) and the trimesic acid in an amount of 11.9 g (0.057 mol).

Subsequently, the metal precursor is supplied to the reaction unit 20 through the first transfer unit 31 and the ligand is supplied to the reaction unit 20 through the second transfer unit 32 . It is characterized in that each of the first and second transfer units use a peristaltic hose pump (a metering supply pump). At this time, the weight ratio of the metal precursor and the ligand supplied to the reaction unit 20 was controlled to be 3:2 (metal precursor: ligand), and the volume of the reaction unit 20 was 0.005 m ³ (maximum retention of the metal precursor and ligand). It was made so that the time could be 2 hours).

After all the metal precursors and ligands were supplied to the reaction unit 20, the reaction was performed for 1 hour (residence time) under conditions of room temperature and 1 bar.

The metal organic framework generated in the reaction section was transferred through a filtering section 40 equipped with a filter having a pore size of 3 microns, and then naturally dried.

As a result, a powdered metal organic framework (Fe-BTC) was obtained.

The yield of the metal organic framework prepared by the above-described apparatus was about 0.02 kg per hour, and the yield relative to the total amount of the metal precursor and the ligand was about 97%.

experimental example. Gas adsorption test

The gas adsorption capacity for ammonia, hydrogen sulfide, or formaldehyde of each of the metal organic frameworks prepared in the Examples was confirmed. Gas adsorption capacity was evaluated using a gas detection tube method. Specifically, after putting 1 g of the metal organic framework prepared in Example into a 5 L reactor and sealing it, the initial concentrations of the test gases (ammonia, hydrogen sulfide and formaldehyde) were set to 50 μmol/mol, 50 μmol/mol and 50 μmol/mol, respectively. It was injected at 20 µmol/mol, and the concentration of the test gas was measured every 30 minutes, and the concentration of the test gas measured after the final 120 minutes was used as the sample concentration. At this time, the test gas concentration was measured with a gas detection tube (SPS-KCLI2218-6218), and the temperature was maintained at 23 ° C and the humidity was 50% (relative humidity) during the test.

The gas adsorption rate (%) was derived from Equation 1 below.

[Equation 1]

Gas adsorption rate (%) = [{(Blank concentration) - (Sample concentration)}/(Blank concentration)] x 100

In Equation 1, the blank concentration means the concentration measured in the same way as the sample concentration in the absence of the metal organic framework prepared in the Example.

As a result, it was confirmed that the ZIF-8 of Example 1 had a gas adsorption rate for hydrogen sulfide of 100% and a gas adsorption rate for formaldehyde of 85%. In addition, the Fe-BTC of Example 2 was able to confirm that the gas adsorption rate for ammonia was 100%, the gas adsorption rate for hydrogen sulfide was 90%, and the gas adsorption rate for formaldehyde was 96%.

The above description of the present invention is for illustrative purposes, and those skilled in the art can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims (13)

As a manufacturing device of a metal organic framework (Metal Organic Framework),
first and second precursor storage units;
a reaction unit synthesizing a metal organic framework by mixing the first and second precursors;
a first transfer unit transferring the precursor from the first precursor storage unit to the reaction unit; and a second transfer unit transferring the precursor from the second precursor storage unit to the reaction unit. and
a filtering unit filtering the metal organic framework synthesized in the reaction unit; including,
The manufacturing apparatus of the metal-organic skeleton, characterized in that consisting of a continuous process.
According to claim 1,
An apparatus for producing a metal organic framework, characterized in that the mixed supply ratio of the second precursor to the first precursor in the reaction unit is 0.1 to 50.
According to claim 1,
An apparatus for producing a metal-organic framework, characterized in that the residence time for synthesizing the metal-organic framework in the reaction unit is 0.1 to 6 hours.
According to claim 1,
An apparatus for producing a metal organic framework, characterized in that the operating temperature of the reaction unit is 10 ° C to 100 ° C.
According to claim 1,
The operating pressure of the reaction unit is -1 to 5 bar, characterized in that, the metal organic skeleton manufacturing apparatus.
According to claim 1,
Characterized in that the first precursor is at least one metal precursor selected from the group consisting of zinc nitrate hexahydrate, iron nitrate nonahydrate, zinc oxide, and combinations thereof , Device for manufacturing a metal organic framework.
According to claim 1,
Preparation of a metal organic framework, characterized in that the second precursor is at least one organic ligand selected from the group consisting of 2-methylimidazole, trimesic acid, and combinations thereof Device.
According to claim 1,
Characterized in that the pore size of the filter of the filtration unit is 0.1 to 5 μm, the manufacturing apparatus of the metal organic framework.
According to claim 1,
The filter of the filtering unit is a replaceable filter, characterized in that, the metal organic framework manufacturing apparatus.
The method according to claim 1, further comprising: a drying unit for drying and pulverizing the metal organic framework filtered by the filtering unit; Characterized in that it further comprises, the manufacturing apparatus of the metal organic framework.
According to claim 1,
An apparatus for producing a metal-organic framework, characterized in that it produces the metal-organic framework at a rate of 0.01 to 0.5 kg/h.
According to claim 1,
An apparatus for producing a metal organic framework having a yield of 95% or more.
As a method for producing a metal organic framework,
Injecting the first and second precursors into the first and second precursor storage units, respectively;
transferring the first and second precursors to a reaction unit;
synthesizing a metal organic framework by mixing the first and second precursors in the reaction unit; and
filtering the synthesized metal organic framework; including,
The manufacturing method of the metal organic framework, characterized in that the manufacturing method is made of a continuous process.

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