WO2023113273A1 - Metal-organic framework for collecting krypton or xenon, and apparatus for collecting krypton or xenon, comprising same - Google Patents

Abstract

The present invention relates to: a metal-organic framework capable of efficiently adsorbing and collecting krypton and/or xenon contained in gas or liquid; and an apparatus for collecting krypton and/or xenon contained in gas or liquid by using the metal-organic framework. The metal-organic framework for collecting krypton and/or xenon, of the present invention, is a metal-organic framework formed from a metal ion comprising copper (Cu) and an organic linker comprising fluorine (F). The metal-organic framework has a flexible structure in which the interplanar structure thereof is not completely fixed by the organic linker, and thus the interplanar distance can be controlled, and the interplanar distance decreases during drying such that nitrogen (N2) is not adsorbed easily and mainly krypton and/or xenon are adsorbed, and thus krypton and/or xenon contained in waste gas, which is generated during a semiconductor process, and also in the air can be efficiently collected.

Description

Metalorganic skeleton for recovering krypton or xenon and apparatus for recovering krypton or xenon including the same

The present invention relates to a metal-organic framework for efficiently recovering krypton and/or xenon, and a device including the metal-organic framework and recovering krypton and/or xenon contained in a fluid.

The present invention is derived from research conducted as part of the research material and diffusion support project of the Science and Technology Job Promotion Agency below.

[Assignment identification number] 1711175880 (2022RMD-S01)

[Name of Department] Ministry of Science and ICT

[Research project name] Research material development and diffusion support project

[Research project title] Development and commercialization of MOF research materials for separation and purification of target gases

[Research management specialized institution] Science and Technology Job Promotion Agency

[Contribution rate] 100%

[Host Research Institution] Sookmyung Women's University

[Research period] 2022.01.01 - 2022.12.31

Krypton (Kr) is mainly used in the lighting industry, such as incandescent light bulbs and automobile lamps, and xenon (Xe) is a rare element mainly used in the aerospace industry, electronic engineering and medicine.

Krypton and xenon are mainly produced from air. Since the amount of krypton and xenon contained in the air (krypton 114 ppmv, xenon 0086 ppmv) is very small, krypton and xenon are very expensive due to the process cost of treating a large amount of air. .

On the other hand, many rare gases are used in the semiconductor manufacturing process. For example, krypton is indispensably used in manufacturing processes such as semiconductor wafers. As described above, since the production cost of krypton is very high, the need to recover and reuse krypton from waste gas used in semiconductor processes is increasing.

An object of the present invention is to collect krypton and/or xenon contained in the air as well as to efficiently recover krypton and/or xenon concentrated in waste gas generated in industrial processes such as semiconductor processes. An object of the present invention is to provide a framework and a krypton or xenon recovery device including the framework.

One aspect of the present invention for achieving the above object is a metal-organic framework composed of a metal ion containing copper (Cu) and an organic linker containing fluorine (F), wherein the interplanar structure of the metal-organic framework is an organic linker. To provide a metal-organic skeleton having a flexible structure that is not completely fixed by

In addition, in the metal-organic framework, one surface and the other surface constituting the interplanar structure may face each other, and copper (Cu) included in the one surface faces CF ₃ of the other surface.

In addition, in the metal-organic framework, the organic linker may include 2,2'-bis (4-carboxyphenyl) hexafluoro-propane. there is.

In addition, the metal organic framework may be formed of, for example, crystal particles (preferably single crystal particles), but is not necessarily limited thereto.

In addition, the metalorganic framework may selectively adsorb or release krypton and/or xenon from a gas containing krypton and/or xenon.

Another aspect of the present invention for achieving the above object is a first container having a suction port for inhaling gas on one side and an outlet for discharging gas on the other side, and a metal-organic skeleton embedded in the first container. A device comprising a sieve, wherein the metal-organic framework is composed of a metal ion containing copper (Cu) and an organic linker containing fluorine (F), and the interplanar structure of the metal-organic framework is completely formed by the organic linker. It is to provide a krypton or xenon recovery device characterized in that it has a flexible (flexible) structure that is not fixed.

In addition, in the krypton or xenon recovery device, the organic linker of the metal-organic framework is 2,2'-bis (4-carboxyphenyl) hexafluoropropane (2,2'-bis (4-carboxyphenyl) hexafluoro- propane).

In addition, in the krypton or xenon recovery device, in the interplanar structure of the metal-organic framework, one surface and the other surface face each other, and copper (Cu) contained in the one surface faces CF ₃ of the other surface. can

In addition, in the krypton or xenon recovery device, the metal-organic skeleton contained in the first container may be in a powder form.

In addition, in the krypton or xenon recovery device, the metal-organic framework may be formed of, for example, crystal particles (preferably single crystal particles), but is not necessarily limited thereto.

In addition, the krypton or xenon recovery device further includes a second container having a suction port for inhaling gas on one side and an outlet for discharging gas on the other side, and the suction port of the second container is formed on the other side. 2 May be connected to the outlet of the vessel.

In addition, in the krypton or xenon recovery device, the metal-organic framework contained in the first container and the metal-organic framework contained in the second container may be of different types.

In addition, in the krypton or xenon recovery device, the metal-organic skeleton contained in the first container and the metal-organic skeleton contained in the second container may be of the same type.

The metalorganic framework according to the present invention can be used for recovery of krypton and/or xenon.

In addition, the metal-organic framework according to an embodiment of the present invention has a flexible structure in which the interplanar structure is not completely fixed by the organic linker, and thus, unlike conventional MOFs, the adsorption amount of nitrogen is reduced while krypton and / or Since it is easy to implement a porous structure capable of increasing the adsorption amount of xenon, the recovery efficiency of krypton and / or xenon can be significantly improved compared to conventionally known MOFs.

In addition, since the MOF having a flexible structure according to an embodiment of the present invention has a property of easily releasing adsorbed xenon, it is possible to more easily separate adsorbed krypton and xenon.

1 is an image of a flexible MOF according to an embodiment of the present invention.

2 shows the results of XRD analysis of a flexible MOF according to an embodiment of the present invention.

3 schematically shows the crystal structure of a flexible MOF according to an embodiment of the present invention.

4 schematically shows the crystal structure of a conventional MOF.

5 is an adsorption and release test result for nitrogen, krypton, and xenon using a flexible MOF according to an embodiment of the present invention.

6 schematically shows the krypton or xenon recovery device.

7 is an adsorption test result for a mixed gas of nitrogen and xenon using a flexible MOF according to an embodiment of the present invention.

8 is a desorption test result for a mixed gas of nitrogen and xenon using a flexible MOF according to an embodiment of the present invention.

9 shows particle images of SBMOF-1, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

10 shows particle images of MOF-303, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

11 shows particle images of Ag@MOF-303, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

12 shows particle images of Cu@MOF-303, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

13 is a particle image of Co-FA, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

14 shows UiO66 particle images, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

15 shows particle images of HKUST-1, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

16 shows XRD analysis results of MOF-74-Co and adsorption and release test results for nitrogen and krypton.

Hereinafter, embodiments of the present application will be described in detail so that those skilled in the art can easily practice with reference to the accompanying drawings. However, the present disclosure may be implemented in many different forms and is not limited to the embodiments described herein.

In addition, in order to clearly describe 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 this specification, when a part is said to be "connected" to another part, this includes not only the case of being "directly connected" but also the case of being "electrically connected" with another element in between. do.

Throughout the present specification, when a member is referred to as being “on,” “above,” “on top of,” “below,” “below,” or “below” another member, this means that a member is located in relation to another member. This includes not only the case of contact but also the case of another member between the two members.

Throughout the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

Throughout the present specification, the term "combination thereof" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It means including one or more selected from the group consisting of.

Throughout this specification, reference to "A and/or B" means "A or B, or A and B".

<Example 1>

Table 1 below shows synthesis conditions of the metal-organic framework according to Example 1 of the present invention.

unit	Cu(NO 3 ) 2 ㆍ3H 2 O	DMF	CPHFP	DMF	Synthesis conditions
mmol	0.0497	-	0.311	-	150 ℃, 20 mL vial
g	0.01200752	2.5 mL	0.12198975	2.5 mL	24h

As shown in Table 1, a first solution is prepared by dissolving 0.012 g of Cu(NO ₃ ) ₂ 3H ₂ O in 2.5 mL of N,N-dimethylmethanamide (DMF). Prepare a second solution by dissolving 0.122 g of CPHFP ((2,2'-bis(4-carboxyphenyl)hexafluoro-propane), an organic ligand, in 2.5 mL of DMF. Then, the first and second solutions are mixed in a 20 mL glass vial. After mixing, it was sufficiently sonicated and reacted for 24 hours in an oven at 120 ° C. After the reaction was completed, it was sufficiently cooled and washed three times with dimethylformamide (DMF) to complete the synthesis process.

1 is an image of a flexible MOF (hereinafter, referred to as “FMOFCu”) synthesized according to an embodiment, and FIG. 2 shows an XRD analysis result of the flexible FMOFCu.

As confirmed in FIGS. 1 and 2, the FMOFCu synthesized under the above conditions was composed of a single crystal and the size of the crystal was about 17 to 20 μm.

As shown in FIG. 3, the FMOFCu synthesized according to the embodiment has a structure in which dimethylformamide is bonded to the end of the interplanar structure and the interplanar structure is not completely fixed by the organic linker, so the interlayer distance It has a flexible structure that can vary the change of

For example, when FMOFCu is dried, the interplanar distance is narrowed, reducing the number of pores in which nitrogen (N ₂ ) can enter and be adsorbed, and the number of pores in which only krypton and xenon can enter are increased, resulting in high-purity separation of krypton and xenon for nitrogen. can be done with

In particular, as shown in FIG. 3, copper (Cu) present in the metal site on one side of the interplanar structure and CF ₃ present on the other side opposite to it have absorption characteristics of krypton and xenon, and the metal site and CF ₃ The space formed by this can adsorb krypton and xenon without adsorbing nitrogen (N ₂ ), thereby enhancing the adsorption characteristics of these gases.

Meanwhile, dimethylformamide bonded to the end of the interplanar structure was removed by washing with ethanol, methanol and/or acetone.

In contrast, in the case of a conventional MOF containing an organic linker having CF ₃ and Cu, as shown in FIG. _Since the number of pores through which N ₂ ) can enter and be adsorbed increases, it is difficult to separate krypton and xenon from nitrogen with high purity, and the amount of adsorption of krypton and xenon is also reduced. Selective separation also makes it difficult.

5 shows adsorption and release test results for nitrogen (N ₂ ), krypton, and xenon using FMOFCu.

As confirmed in FIG. 5 , in the case of FMOFCu prepared according to an embodiment of the present invention, it can be seen that the adsorption amount of xenon and krypton is significantly higher than that of nitrogen (N ₂ ). Xenon and krypton can be selectively separated from nitrogen (N ₂ ) by using the difference in adsorption amount. In addition, in the case of xenon, since emission is easy, there may be an advantage in that xenon can be separated with high purity from krypton, xenon, and some nitrogen (N ₂ ) adsorbed together.

6 schematically shows the krypton or xenon recovery device. The recovery device of FIG. 6 is for separating xenon and krypton from a gas in which xenon and krypton are mixed.

As shown in FIG. 6, the krypton or xenon recovery device is connected to a first container having a suction port for inhaling gas on one side and an outlet for discharging gas on the other side, and the outlet of the first container. It may be made of a second container including a suction port formed on the side and a discharge port for discharging gas on the other side.

The first container may contain pellets made of a metal-organic framework to more easily adsorb xenon, and the second container may contain pellets made of a metal-organic framework to more easily adsorb krypton.

At this time, since the metalorganic framework according to the embodiment adsorbs both xenon and krypton well, after passing through the first container under a condition in which xenon is relatively easily adsorbed, the second container is opened in a condition in which krypton is easily adsorbed. It is also possible to separate krypton and xenon included in the mixed gas by using a passing method.

7 is an adsorption test result for a mixed gas of nitrogen and xenon using FMOFCu.

In the adsorption test for the mixed gas of nitrogen and xenon, after loading 5 g of FMOFCu in a sample bed with a diameter of 0.5 inch × 10 cm, 5 sccm at 760 torr (Fig. 7 (a)), 10 sccm (Fig. 7 (b)), When xenon and nitrogen flowed through the inlet of the sample bed at a flow rate of 20 sccm (FIG. 7(c)), a method of measuring detection amounts of nitrogen and xenon at the outlet of the sample bed was used. At this time, pretreatment was performed on the sample bed at 100° C. in a vacuum for about 2 hours.

As confirmed in FIG. 7 , xenon is hardly detected for about 7,209 seconds at 5 sccm, for about 7,043 seconds at 10 sccm, and for 3,765 seconds at a flow rate of 20 sccm, and then the amount of xenon detected tends to increase. In addition, as the flow rate increases, the adsorption rate tends to increase. In contrast, nitrogen was continuously detected in a significant amount from the beginning. That is, it can be seen that xenon is selectively adsorbed by the FMOFCu loaded into the sample bed. Through this selective adsorption function, it is possible to separate xenon from industrial waste gas.

8 is a desorption test result for a mixed gas of nitrogen and xenon using FMOFCu.

The desorption test was carried out in two cases: the case of adsorption of xenon at 120 ° C, followed by nitrogen gas flow and desorption (black circle), and the case of xenon gas flow and desorption (gray circle).

As confirmed in FIG. 8 , the case of desorption while flowing xenon gas (gray circle) was superior to the case of desorption while flowing nitrogen gas (black circle).

<Comparative Example 1>

9 shows particle images of SBMOF-1, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

As confirmed in the adsorption and release test results of FIG. 9, SBMOF-1 is also capable of selective adsorption of krypton compared to nitrogen, but is significantly lower than the sum of the adsorption amounts of krypton (Kr) and xenon (Xe) in the embodiment and is selective. Separation is poor.

<Comparative Example 2>

10 shows particle images of MOF-303, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

As confirmed in the adsorption and release test results of FIG. 10, MOF-303 is also capable of selectively adsorbing krypton compared to nitrogen, but is significantly lower than the sum of the adsorption amounts of krypton (Kr) and xenon (Xe) in the embodiment. Separation is poor.

<Comparative Example 3>

11 shows particle images of Ag@MOF-303, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

As confirmed in the adsorption and release test results of FIG. 11, Ag@MOF-303 can also selectively adsorb krypton compared to nitrogen, but significantly more than the sum of the adsorption amounts of krypton (Kr) and xenon (Xe) in the example. low and poor selective separability.

<Comparative Example 4>

12 shows particle images of Cu@MOF-303, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

As confirmed in the adsorption and release test results of FIG. 12, Cu@MOF-303 can also selectively adsorb krypton compared to nitrogen, but significantly more than the sum of the adsorption amounts of krypton (Kr) and xenon (Xe) in the embodiment. low and poor selective separability.

<Comparative Example 5>

13 is a particle image of Co-FA, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

As confirmed in the adsorption and release test results of FIG. 13, Co-FA is also capable of selective adsorption of krypton compared to nitrogen, but is significantly lower than the sum of the adsorption amounts of krypton (Kr) and xenon (Xe) in the embodiment and is selective. Separation is poor.

<Comparative Example 6>

14 shows UiO66 particle images, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

As confirmed in the adsorption and release test results of FIG. 14, UiO66 can also selectively adsorb krypton compared to nitrogen, but the selective separability is significantly lower than the sum of the adsorption amounts of krypton (Kr) and xenon (Xe) in the embodiment. it falls

<Comparative Example 7>

15 shows particle images of HKUST-1, XRD analysis results, and adsorption and release test results for nitrogen and krypton.

As confirmed from the adsorption and release test results of FIG. 15, HKUST-1 is also capable of selective adsorption of krypton compared to nitrogen, but is significantly lower than the sum of the adsorption amounts of krypton (Kr) and xenon (Xe) in the example and selectively Separation is poor.

<Comparative Example 8>

16 shows XRD analysis results of MOF-74-Co and adsorption and release test results for nitrogen and krypton.

As confirmed in the adsorption and release test results of FIG. 16, MOF-74-Co can also selectively adsorb krypton compared to nitrogen, but significantly more than the sum of the adsorption amounts of krypton (Kr) and xenon (Xe) in the example. low and poor selective separability.

The above description of the present application is for illustrative purposes, and those skilled in the art will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. 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 application is indicated by the following claims rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts thereof should be construed as being included in the scope of the present application.

Claims (9)

1. A metal-organic skeleton composed of a metal ion containing copper (Cu) and an organic linker containing fluorine (F),

   A metal-organic skeleton having a flexible structure in which the interplanar structure of the metal-organic skeleton is not completely fixed by an organic linker.
2. According to claim 1,

   In the interplanar structure, one side and the other side face each other,

   Copper (Cu) contained on the one surface has a structure facing CF ₃ on the other surface, the metal-organic framework.
3. According to claim 1,

   The organic linker comprises 2,2'-bis (4-carboxyphenyl) hexafluoropropane (2,2'-bis (4-carboxyphenyl) hexafluoro-propane).
4. According to claim 1,

   The metal-organic framework is composed of crystal particles, the metal-organic framework.
5. According to claim 1,

   Wherein the metal-organic framework selectively adsorbs or releases krypton and/or xenon from a gas containing krypton and/or xenon.
6. A first container having a suction port for inhaling gas on one side and an outlet for discharging gas on the other side;

   A device comprising a metal-organic skeleton embedded in the first container,

   The metal-organic skeleton is an apparatus for recovering krypton or xenon, including one according to any one of claims 1 to 5.
7. According to claim 6,

   The krypton or xenon recovery device,

   A second container having a suction port for inhaling gas on one side and an outlet for discharging gas on the other side;

   Including a metal-organic skeleton embedded in the second container,

   The inlet of the second container is connected to the outlet of the second container, krypton or xenon recovery device.
8. According to claim 7,

   The metal-organic skeleton contained in the first container and the metal-organic skeleton contained in the second container are of different types.
9. According to claim 7,

   The metal-organic skeleton contained in the first container and the metal-organic skeleton contained in the second container are of the same type, krypton or xenon recovery device.

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