High-purity electronic special gas storage and separation method

Abstract

The invention discloses a high-purity electronic special gas storage and separation method, and belongs to the technical field of chemical adsorption, and the method comprises the following steps: contacting an adsorption medium with electronic special gas to realize high-capacity storage of the electronic special gas; or, the adsorption medium is in contact with the mixed gas containing the electronic special gas, so that the electronic special gas is separated and purified; the adsorption medium is an ordered three-dimensional microporous metal organic framework material formed by coordination construction of Co < 2 + >, Zn < 2 + > or Fe < 2 + > and 1, 5-dihydrobenzo [1, 2-d: 4, 5-d '] bis ([1, 2, 3] triazole) or 1, 7-dihydrodibenzo [b, e] [1, 4] dioxin [2, 3-d: 7, 8-d'] bis ([1, 2, 3] triazole). According to the invention, efficient storage, separation and purification of electronic special gases such as SF6, NF3, C3F6, CF4, BF3, C2F6, C3F8, CHF3, CF3I, C2F5I, SiH4, Si2H6, AsH3, GeF4, BCl3, WF6, AsF3, ClF3 and the like can be realized, and through metal ion exchange and metal cluster coordination functional group modulation, regulation and control of pore size and change of pore chemical environment can be realized, so that specific electronic special gas guest molecules can be accurately identified, and efficient storage, separation and preparation of high-purity electronic special gases can be realized.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical adsorption, and relates to an adsorption method for electronic special gases, and in particular to a storage and separation method for high-purity electronic special gases. Background Art

[0002] High-purity electronic special gases have important applications in high-end manufacturing fields such as semiconductors, liquid crystal displays, photovoltaics, and optoelectronic devices. Due to its excellent chemical stability and etching selectivity, it is widely used in chip etching and cleaning processes. For example, SF6 is commonly used in deep silicon etching processes and can provide high anisotropic etching effects; NF3 is the main source of plasma etching gas and CVD chamber cleaning; CF4 is used to etch silicon-containing materials and provide good etching directionality; BF3 can be used as a dopant to prepare P-type semiconductors. In order to ensure precise control in key process links such as etching, deposition, and doping, and to avoid electrical, optical, or structural defects caused by impurities, the purity of electronic special gases is usually required to reach 99.999% or even 99.9999%. At present, the industry mainly uses cryogenic distillation or solvent extraction technology to obtain high-purity electronic special gases, which has high energy consumption and is difficult to meet the gas purity requirements of high-end applications. Therefore, how to achieve efficient separation and recovery of electronic special gases has become a key issue that needs to be urgently solved in the electronic special gas industry and materials science field.

[0003] Metal-organic framework materials have shown certain potential in the field of electronic specialty gas adsorption and separation due to their unique designable metal nodes, organic ligands and highly adjustable pore structures. For example, the separation selectivity of Zn-bzc-CF3 MOF for C3F6 / C3F8 can reach 12, but the adsorption capacity of C3F6 is only 47cm 3 / g (Angew.Chem.Int.Ed.2024,63,e202401770); the invention patent application with publication number CN 118580504 A discloses a microporous MOFs material (CTGU-47-Mn) that can be used to capture SF6 in SF6 / N2 mixed gas, but does not show the ability to separate other electronic special gases. In general, the application of metal organic framework materials in the field of electronic special gas separation is still in the primary exploration stage, and the adsorption capacity and separation selectivity still need to be improved.

[0004] In addition, high-purity electronic specialty gases usually rely on high-pressure steel cylinders or cryogenic storage technologies during storage and transportation. However, traditional storage and transportation methods have problems such as low volume utilization rate and high energy consumption, and the gas purity is extremely vulnerable to the influence of the external environment. In addition, for corrosive electronic specialty gases such as BF3, NF3, AsH3, and GeF4, specific high-end customized high-pressure gas cylinders are required for storage, and the gas cylinder pressure is as high as 10-100 MPa. Once leakage or container breakage occurs, serious safety problems will be brought. Therefore, it is necessary to develop a method for efficient and safe storage of dangerous electronic specialty gases. Summary of the Invention

[0005] The present invention provides a method for storing and separating high-purity electronic specialty gases to overcome the defects of the prior art.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A method for storing and separating high-purity electronic specialty gases: contacting an adsorption medium with an electronic specialty gas to achieve the storage of the electronic specialty gas; or, contacting the adsorption medium with a mixed gas containing an electronic specialty gas to achieve the separation of the electronic specialty gas; the adsorption medium is an ordered three-dimensional microporous metal-organic framework material formed by coordination of Co 2+ , Zn 2+ or Fe 2+ with 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) or 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole).

[0008] Among them, the structural formula of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is The structural formula of 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole) is

[0009]

[0010] To optimize the above technical solution, the specific measures taken also include:

[0011] Further, the preparation method of the microporous metal-organic framework is: mixing Co 2+ , 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) with a solvent, and heating at 80-160 °C for 24-72 h to obtain a Co 2+ microporous metal-organic framework material; mixing Zn 2+, 1,7 - Dihydrodibenzo[b,e][1,4]dioxino[2,3 - d:7,8 - d']bis([1,2,3]triazole) is mixed with a solvent and heated at 100 - 160 °C for 24 - 72 h to obtain Zn 2+ microporous metal - organic framework material; Fe 2+ , 1,5 - Dihydrobenzo[1,2 - d:4,5 - d']bis([1,2,3]triazole) is mixed with a solvent and then an acid is added, and it is heated at 70 - 120 °C for 24 - 72 h to obtain Fe 2+ microporous metal - organic framework material; The solvent is one or more of N,N - dimethylformamide solution, methanol, and water; The acid is one or more of hydrochloric acid, nitric acid, and sulfuric acid.

[0012] Among them, the Co 2+ microporous metal - organic framework material and the Zn 2+ microporous metal - organic framework material have the same topological structure, both are metal - cluster - based cubic metal - organic frameworks with Kuratowski configuration; The Fe 2+ microporous metal - organic framework material is a hexagonal metal - organic framework.

[0013] Furthermore, in the preparation method of the Co 2+ microporous metal - organic framework material, the molar ratio of Co 2+ to 1,5 - Dihydrobenzo[1,2 - d:4,5 - d']bis([1,2,3]triazole) is 1 - 10:1; The dosage ratio of Co 2+ to the solvent is 1 mmol:5 - 20 mL; In the preparation method of the Zn 2+ microporous metal - organic framework material, the molar ratio of Zn 2+ to 1,7 - Dihydrodibenzo[b,e][1,4]dioxino[2,3 - d:7,8 - d']bis([1,2,3]triazole) is 1 - 10:1; The dosage ratio of Zn 2+ to the solvent is 1 mmol:5 - 20 mL; In the preparation method of the Fe 2+ microporous metal - organic framework material, the molar ratio of Fe 2+ to 1,5 - Dihydrobenzo[1,2 - d:4,5 - d']bis([1,2,3]triazole) is 1 - 10:1; The dosage ratio of Fe 2+ , the solvent and the acid is 1 mmol:5 - 20 mL:0.1 - 1 mL.

[0014] Furthermore, the microporous metal - organic framework adjusts the pore window size by exchanging metal ions or modulating the coordination functional groups of metal clusters, and at the same time changes the chemical environment inside the pores; The pore window size of the Co 2+ microporous metal - organic framework material before and after adjustment is Zn 2+ The pore window sizes of the microporous metal-organic framework material before and after regulation are Fe 2 + The pore window sizes of the microporous metal-organic framework material before and after regulation are

[0015] Furthermore, the metal ion is Zn 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mn 2+ , Mg 2+ , Fe 2+ , Ca 2+ , Cu + , Li + or any one or more of them; the metal cluster coordination functional group is any one or more of CH3, NH2, F, I, Br, OH, CN, COOH, OCH3.

[0016] Furthermore, the method for exchanging metal ions is: immersing the microporous metal-organic framework material in a metal salt solution and stirring at 25 - 90 °C for 0.25 - 12 h to obtain the microporous metal-organic framework after exchanging metal ions; the metal salt in the metal salt solution is the chloride, nitrate or sulfate of the metal ion; the method for modulating the metal cluster coordination functional group is: immersing the microporous metal-organic framework material or the microporous metal-organic framework after exchanging metal ions in a salt solution containing the metal cluster coordination functional group and stirring at 25 - 90 °C for 0.25 - 12 h to obtain the microporous metal-organic framework after modulating the metal cluster coordination functional group; the metal cluster coordination functional group salt in the metal cluster coordination functional group salt solution is the lithium salt, sodium salt, potassium salt or cesium salt containing the metal cluster coordination functional group; the solvents in the metal salt solution and the metal cluster coordination functional group salt solution are one or more of N,N-dimethylformamide, N,N-dimethylacetamide, methanol, water, dimethyl sulfoxide.

[0017] Furthermore, in the metal salt solution, the dosage ratio of the metal salt to the solvent is 2 - 3 mmol∶10 - 20 mL; in the metal cluster coordination functional group salt solution, the dosage ratio of the metal cluster coordination functional group salt to the solvent is 2 - 3 mmol∶10 - 20 mL.

[0018] Further, the electronic special gas is SF6, NF3, C3F6, CF4, BF3, C2F6, C3F8, CHF3, CF3I, C2F5I, SiH4, Si2H6, BCl3, WF6, AsF3, ClF3, AsH3 or GeF4; the mixed gas containing the electronic special gas is a binary, ternary or quaternary mixed gas, and the volume ratio of each component is 1-99. Preferably, the volume ratio of each component in the binary mixed gas is 1:1-99, and the volume ratio of each component in the ternary mixed gas is 1:1-20:1-80.

[0019] Further, using the Co 2+ microporous metal-organic framework material as an adsorption medium for separating the C3F6 and C3F8 mixed gas; Co 2+ The pore window size of the microporous metal-organic framework material is The purity of the separated C3F6 and C3F8 is greater than 99.9999%; using the Co 2+ after exchanging Ni 2+ microporous metal-organic framework material as an adsorption medium for separating the CF4 and NF3 mixed gas; after exchanging Ni 2+ Co 2+ The pore window size of the microporous metal-organic framework material is The purity of the separated CF4 and NF3 is greater than 99.99%; using the Co + after exchanging Cu 2+ microporous metal-organic framework material as an adsorption medium for storing NF3; after exchanging Cu + Co 2+ The pore window size of the microporous metal-organic framework material is The adsorption storage capacity of NF3 can reach 30.0 wt%, and the release rate at 0.1 bar is 63.2%; using the Co 2+ after modulating F as an adsorption medium for separating the C2F6 and CF4 mixed gas; Co 2+ after modulating F, the pore window size of the microporous metal-organic framework material is The purity of the separated C2F6 and CF4 is greater than 99.999%; using the Zn 2+ after modulating OH as an adsorption medium for storing BF3; Zn 2+ after modulating OH, the pore window size of the microporous metal-organic framework material is The adsorption storage capacity of BF3 can reach 68.0 wt%, and the release rate at 0.1 bar is 70.6%; using the Co 2+ after modulating OH as an adsorption medium for storing AsH3; Co 2+ after modulating OH, the pore window size of the microporous metal-organic framework material is The adsorption storage capacity for AsH3 can reach 33.0 wt%, and the release rate at 0.1 bar is 87.8%; using the Zn 2+ microporous metal-organic framework material as the adsorption medium for separating the SF6 and N2 mixed gas; Zn 2+ The pore window size of the microporous metal-organic framework material is The purities of the separated SF6 and N2 are greater than 99.99%; using the Zn + after Li exchange 2+ microporous metal-organic framework material as the adsorption medium for storing C3F6; after Li exchange + Zn 2+ The pore window size of the microporous metal-organic framework material is The adsorption storage capacity for C3F6 can reach 147.0 wt%, and the release rate at 0.1 bar is 77.8%; using the Fe 2+ microporous metal-organic framework material as the adsorption medium for separating the CF4 and N2 mixed gas; Fe 2+ The pore window size of the microporous metal-organic framework material is The purities of the separated CF4 and N2 are greater than 99.99%; using the Fe 2+ after F modulation 2+ microporous metal-organic framework material as the adsorption medium for storing GeF4; Fe after F modulation

[0020] The adsorption storage capacity for GeF4 can reach 42.0 wt%, and the release rate at 0.1 bar is 81.2%.

[0020] Furthermore, the storage method is: filling the electronic special gas into a negative pressure tank filled with spherical, columnar, strip-shaped or block-shaped microporous metal-organic framework materials; the adsorption operation pressure is 0.3 - 1 bar, and the desorption release pressure is 0.1 - 0.8 bar; the storage capacity of the electronic special gas is 10 - 180 wt%, and the desorption rate > 60%. The separation method is fluidized bed adsorption, moving bed adsorption or fixed bed adsorption; the adsorption method is temperature swing adsorption, pressure swing adsorption or temperature-pressure swing coupling adsorption; the operation temperature is -40 - 100 °C, and the operation pressure is 0.05 - 60 bar. Preferably, the adsorption is at room temperature, the desorption is at 60 - 100 °C, or the adsorption is at normal pressure, and the desorption is at 0.05 - 0.1 bar; the purity of the electronic special gas obtained after separation is 99.99 - 99.9999%.

[0021] The beneficial effects of the present invention are as follows:

[0022] 1. Compared with traditional adsorbents, the microporous metal-organic framework material of the present invention can exchange metal ions or change the types of metal cluster coordination functional groups after simple synthesis, thereby precisely controlling the pore window size and the chemical environment inside the pores. Specifically, the pore size can be precisely regulated within the sub-angstrom scale to be close to the size of the target guest molecule; through the precise design of the chemical environment inside the pores, the matching between the electrostatic potential within the framework and the guest molecule can be achieved, thereby significantly enhancing the interaction force with the more polar target guest molecule, and ultimately achieving the purpose of efficient storage and selective separation and purification of high-purity electronic special gases at room temperature.

[0023] 2. The microporous metal-organic framework material of the present invention is easy to regenerate, has high structural stability, corrosion resistance, and a long service life. While improving the storage and separation capabilities, it can also take into account the stability and operability of the production process, and has good industrial application prospects.

[0024] 3. The present invention can efficiently adsorb various electronic special gases such as SF6, NF3, C3F6, CF4, BF3, C2F6, C3F8, CHF3, CF3I, C2F5I, SiH4, Si2H6, BCl3, WF6, AsF3, ClF3, AsH3, GeF4, etc., so as to achieve the storage and separation of electronic special gases. The highest purity after separation can reach 99.99999%, and it has excellent storage capacity and release rate. In addition, compared with the traditional cryogenic distillation technology or solvent extraction technology in the industry, the method for separating and purifying electronic special gases of the present invention has outstanding advantages such as low energy consumption, easy operation, and small equipment investment. Description of the Drawings

[0025] Figure 1 is Co of Example 1 2+ Adsorption isotherm diagram of the microporous metal-organic framework material for C3F6 and C3F8 at 25°C;

[0026] Figure 2 is Cu of Example 3 2+ Adsorption isotherm diagram of the microporous metal-organic framework material for NF3 at 25°C;

[0027] Figure 3 is Mg of Example 6 2+ Adsorption isotherm diagram of the microporous metal-organic framework material for C3F6 and CF4 at 25°C;

[0028] Figure 4 is Co after modulating F of Example 8 2+ Adsorption isotherm diagram of the microporous metal-organic framework material for C2F6 and CF4 at 25°C;

[0029] Figure 5 is Co after modulating OH of Example 9 2+Adsorption isotherm diagram of micro-porous metal-organic framework materials for AsH3 at 25 °C;

[0030] Figure 6 is Zn of Example 10 2+ Adsorption isotherm diagram of micro-porous metal-organic framework materials for SF6 and N2 at 25 °C;

[0031] Figure 7 is Li of Example 11 + Adsorption isotherm diagram of micro-porous metal-organic framework materials for C3F6 at 25 °C;

[0032] Figure 8 is Fe of Example 12 2+ Adsorption isotherm diagram of micro-porous metal-organic framework materials for CF4 and N2 at 25 °C. Detailed implementation manners

[0033] The present invention will be further described below in conjunction with specific embodiments.

[0034] Example 1

[0035] This example provides a method for separating high-purity electronic special gases: contacting an adsorption medium with a mixed gas containing electronic special gases to achieve the separation of electronic special gases.

[0036] The adsorption medium is Co 2+ micro-porous metal-organic framework material, and its preparation method is: putting 0.8 mmol of CoCl2 and 0.4 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) into a culture bottle, adding 8 mL of N,N-dimethylformamide, ultrasonically treating at room temperature for 5 min, and then reacting at 100 °C for 48 h to obtain.

[0037] Test the adsorption behavior of the Co 2+ micro-porous metal-organic framework material after activation in this example for C3F6 and C3F8 at 25 °C, and its adsorption isotherm is as Figure 1 shown. The adsorption amount of Co 2+ micro-porous metal-organic framework material for C3F6 is 80.8 cm 3 / g, and the adsorption amount for C3F8 is only 1.1 cm 3 / g. Therefore, the mixed gas of C3F6 and C3F8 can be efficiently separated and purified. After separation by temperature swing adsorption (adsorbing at room temperature and desorbing at 60-100 °C), C3F6 and C3F8 with a purity of 99.9999% can be obtained.

[0038] Example 2

[0039] This embodiment provides a method for storing and separating high-purity electronic special gases: contacting an adsorption medium with the electronic special gas to achieve the storage of the electronic special gas; or, contacting the adsorption medium with a mixed gas containing the electronic special gas to achieve the separation of the electronic special gas.

[0040] The adsorption medium is Ni 2+ microporous metal-organic framework material, and its preparation method is: placing 0.8 mmol of CoCl2 and 0.4 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a culture flask, adding 10 mL of methanol, ultrasonically treating at room temperature for 5 min, and then reacting at 120 °C for 48 h to obtain Co 2+ microporous metal-organic framework material. Immerse the Co 2+ microporous metal-organic framework material into 20 mL of an N,N-dimethylacetamide solution containing 2 mmol of NiCl2, and stir at 60 °C for 30 min to obtain the Co 2+ after Ni exchange 2+ microporous metal-organic framework material, that is, Ni 2+ microporous metal-organic framework material.

[0041] Example 3

[0042] This embodiment provides a method for storing high-purity electronic special gases: contacting an adsorption medium with the electronic special gas to achieve the storage of the electronic special gas.

[0043] The adsorption medium is Cu 2+ microporous metal-organic framework material, and its preparation method is: placing 0.8 mmol of CoCl2 and 0.4 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a culture flask, adding 10 mL of methanol, ultrasonically treating at room temperature for 5 min, and then reacting at 120 °C for 48 h to obtain Co 2+ microporous metal-organic framework material. Immerse the Co 2+ microporous metal-organic framework material into 20 mL of an N,N-dimethylacetamide solution containing 2 mmol of CuCl2, and stir at 60 °C for 30 min to obtain the Cu 2+ after exchange 2+ microporous organic framework material, that is, Cu 2+ microporous metal-organic framework material.

[0044] Test the adsorption behavior of the activated Cu 2+ microporous metal-organic framework material for NF3 at 25 °C, and its adsorption isotherm is as Figure 2 shown. The adsorption amount of the Cu 2+ microporous metal-organic framework material for NF3 is 94.9 cm 3 / g, the adsorption storage capacity can reach 30.0 wt%, enabling high-capacity storage of NF3, and the release rate at 0.1 bar is 63.2%.

[0045] Example 4

[0046] This example provides a method for storing and separating high-purity electronic special gases: contacting the adsorption medium with the electronic special gas to achieve the storage of the electronic special gas; or, contacting the adsorption medium with a mixed gas containing the electronic special gas to achieve the separation of the electronic special gas.

[0047] The adsorption medium is Fe 2+ microporous metal-organic framework material, and its preparation method is: placing 1 mmol of CoCl2 and 0.5 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a culture flask, adding 2.5 mL of methanol and 7.5 mL of N,N-dimethylformamide, ultrasonically treating at room temperature for 5 min, and then reacting at 120 °C for 24 h to obtain Co 2+ microporous metal-organic framework material. Immerse the Co 2+ microporous metal-organic framework material into a 20 mL methanol solution containing 2 mmol of FeCl2, stir at 40 °C for 30 min to obtain the exchanged Fe 2+ Co 2+ microporous metal-organic framework material, that is, Fe 2+ microporous metal-organic framework material.

[0048] Example 5

[0049] This example provides a method for storing and separating high-purity electronic special gases: contacting the adsorption medium with the electronic special gas to achieve the storage of the electronic special gas; or, contacting the adsorption medium with a mixed gas containing the electronic special gas to achieve the separation of the electronic special gas.

[0050] The adsorption medium is Mn 2+ microporous metal-organic framework material, and its preparation method is: placing 1 mmol of CoCl2 and 0.5 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene liner, adding 2.5 mL of methanol and 7.5 mL of N,N-dimethylformamide, ultrasonically treating at room temperature for 5 min, and then reacting at 140 °C for 24 h to obtain Co 2+ microporous metal-organic framework material. Immerse the Co 2+ microporous metal-organic framework material into a 10 mL N,N-dimethylacetamide solution containing 2 mmol of MnCl2, stir at 50 °C for 60 min to obtain the exchanged Mn 2+ Co 2+ microporous metal-organic framework material, that is, Mn 2+Microporous metal-organic framework materials.

[0051] Example 6

[0052] This example provides a method for separating high-purity electronic special gases: contacting an adsorption medium with a mixed gas containing electronic special gases to achieve the separation of electronic special gases.

[0053] The adsorption medium is Mg 2+ microporous metal-organic framework material, and its preparation method is: placing 1.5 mmol of CoCl2 and 0.5 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, adding 10 mL of N,N-dimethylformamide, ultrasonically treating at room temperature for 5 min, and then reacting at 160 °C for 48 h to obtain Co 2+ microporous metal-organic framework material. Immerse Co 2+ microporous metal-organic framework material into 15 mL of N,N-dimethylacetamide solution containing 3 mmol of MgCl2, stir at 50 °C for 60 min to obtain the exchanged Mg 2+ after Co 2+ microporous metal-organic framework material, that is, Mg 2+ microporous metal-organic framework material.

[0054] Test the adsorption behavior of the activated Mg 2+ microporous metal-organic framework material for C3F6 and CF4 at 25 °C. Its adsorption isotherm is as Figure 3 shown. The adsorption capacity of Mg 2+ microporous metal-organic framework material for C3F6 is 64.2 cm 3 / g, and the adsorption capacity for CF4 is only 5.0 cm 3 / g. Therefore, the mixed gas of C3F6 and CF4 can be efficiently separated and purified. After separation by temperature swing adsorption (adsorption at room temperature, desorption at 60-100 °C), C3F6 and CF4 with a purity of 99.999% can be obtained.

[0055] Example 7

[0056] This example provides a method for storing and separating high-purity electronic special gases: contacting an adsorption medium with electronic special gases to achieve the storage of electronic special gases; or, contacting an adsorption medium with a mixed gas containing electronic special gases to achieve the separation of electronic special gases.

[0057] The adsorption medium is Li +Microporous metal-organic framework material, and its preparation method: Place 1.5 mmol of CoCl2 and 0.5 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add 10 mL of N,N-dimethylformamide, ultrasonically treat at room temperature for 5 min, and then react at 150 °C for 48 h to obtain Co 2+ Microporous metal-organic framework material. Immerse the Co 2+ Microporous metal-organic framework material in 15 mL of N,N-dimethylacetamide solution containing 3 mmol of LiCl, stir at 50 °C for 60 min to obtain the Co + after Li 2+ exchange Microporous metal-organic framework material, that is, Li + Microporous metal-organic framework material.

[0058] Example 8

[0059] This example provides a method for separating high-purity electronic special gases: contacting an adsorption medium with a mixed gas containing electronic special gases to achieve the separation of electronic special gases.

[0060] The adsorption medium is a microporous metal-organic framework material with the metal cluster coordination functional group modulated to F, and its preparation method: Place 1.5 mmol of CoCl2 and 0.5 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add 10 mL of N,N-dimethylformamide, ultrasonically treat at room temperature for 5 min, and then react at 140 °C for 48 h to obtain Co 2+ Microporous metal-organic framework material. Immerse the Co 2+ Microporous metal-organic framework material in 20 mL of aqueous solution containing 3 mmol of cesium fluoride, stir at room temperature for 6 h to obtain the Co 2+ after modulating F Microporous metal-organic framework material.

[0061] Test the adsorption behavior of the Co 2+ microporous metal-organic framework material after modulating F and activating in this example for C2F6 and CF4 at 25 °C, and its adsorption isotherm is as Figure 4 shown. The adsorption capacity of the Co 2+ microporous metal-organic framework material after modulating F for C2F6 is 79.1 cm 3 / g, and the adsorption capacity for CF4 is only 42.4 cm 3 / g. Therefore, the mixed gas of C2F6 and CF4 can be efficiently separated and purified. After separation by temperature swing adsorption (adsorption at room temperature, desorption at 60 - 100 °C), C2F6 and CF4 with a purity of 99.999% can be obtained.

[0062] Example 9

[0063] This embodiment provides a method for storing high-purity electronic special gases: contacting an adsorption medium with the electronic special gases to achieve the storage of the electronic special gases.

[0064] The adsorption medium is a microporous metal-organic framework material with metal cluster coordination functional groups modulated to OH, and its preparation method is as follows: Place 1.5 mmol of CoCl2 and 0.5 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add 10 mL of N,N-dimethylformamide, ultrasonicate at room temperature for 5 min, and then react at 140 °C for 48 h to obtain Co 2+ microporous metal-organic framework material. Immerse the Co 2+ microporous metal-organic framework material in 20 mL of a methanol solution containing 3 mmol of lithium hydroxide, and stir at room temperature for 12 h to obtain the Co 2+ microporous metal-organic framework material after modulating to OH.

[0065] Test the adsorption behavior of the Co 2+ microporous metal-organic framework material after modulating to OH and activating in this embodiment for AsH3 at 25 °C. Its adsorption isotherm is as Figure 5 shown. The adsorption capacity of the Co 2+ microporous metal-organic framework material after modulating to OH for AsH3 is 94.5 cm 3 / g, and the adsorption storage capacity can reach 33.0 wt%, enabling high-capacity storage of AsH3, and the release rate at 0.1 bar is 87.8%.

[0066] Example 10

[0067] This embodiment provides a method for separating high-purity electronic special gases: contacting an adsorption medium with a mixed gas containing the electronic special gases to achieve the separation of the electronic special gases.

[0068] The adsorption medium is Zn 2+ microporous metal-organic framework material, and its preparation method is as follows: Place 1.5 mmol of ZnCl2 and 0.5 mmol of 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add 10 mL of N,N-dimethylformamide, ultrasonicate at room temperature for 5 min, and then react at 140 °C for 48 h to obtain Zn 2+ microporous metal-organic framework material.

[0069] Test the adsorption behavior of the Zn 2+ microporous metal-organic framework material after activating in this embodiment for SF6 and N2 at 25 °C. Its adsorption isotherm is as Figure 6 shown. Zn2+ The adsorption capacity of the microporous metal-organic framework material for SF6 is 92.4 cm 3 / g, and the adsorption capacity for N2 is only 10.0 cm 3 / g. Therefore, it can efficiently separate and purify the SF6 and N2 mixed gas. After separation by temperature swing adsorption (adsorption at room temperature and desorption at 60 - 100 °C), SF6 and N2 with a purity of 99.99% can be obtained.

[0070] Example 11

[0071] This example provides a method for storing high-purity electronic special gases: contacting the adsorption medium with the electronic special gas to achieve the storage of the electronic special gas.

[0072] The adsorption medium is Li + microporous metal-organic framework material, and its preparation method is as follows: Place 1.5 mmol of ZnCl2 and 0.5 mmol of 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add 10 mL of N,N-dimethylformamide, ultrasonicate at room temperature for 5 min, and then react at 145 °C for 48 h to obtain Zn 2+ microporous metal-organic framework material. Immerse the Zn 2+ microporous metal-organic framework material in 20 mL of an N,N-dimethylacetamide solution containing 3 mmol of LiCl, stir at 50 °C for 60 min to obtain the exchanged Li + Zn 2+ microporous metal-organic framework material, that is, Li + microporous metal-organic framework material.

[0073] Test the adsorption behavior of the activated Li + microporous metal-organic framework material for C3F6 at 25 °C. Its adsorption isotherm is as Figure 7 shown. The adsorption capacity of the Li + microporous metal-organic framework material for C3F6 is 220.2 cm 3 / g, the adsorption storage capacity can reach 147.0 wt%, it can store C3F6 with high capacity, and the release rate at 0.1 bar is 77.8%.

[0074] Example 12

[0075] This example provides a method for separating high-purity electronic special gases: contacting the adsorption medium with the mixed gas containing the electronic special gas to achieve the separation of the electronic special gas.

[0076] The adsorption medium is Fe 2+Microporous metal-organic framework material, and its preparation method is as follows: Put 1.0 mmol of FeCl2 and 0.5 mmol of 1,7-dihydrodibenzo[b,e][1,4]dioxino[2,3-d:7,8-d']bis([1,2,3]triazole) into a culture bottle, add 10 mL of N,N-dimethylformamide, ultrasonicate at room temperature for 5 min, then add 0.1 mL of hydrochloric acid, and react at 100 °C for 48 h to obtain Fe 2+ microporous metal-organic framework material.

[0077] Test the adsorption behavior of the activated Fe 2+ microporous metal-organic framework material for CF4 and N2 at 25 °C. Its adsorption isotherm is as Figure 8 shown. Fe 2+ The adsorption capacity of the microporous metal-organic framework material for CF4 is 69.7 cm 3 / g, and the adsorption capacity for N2 is only 7.6 cm 3 / g. Therefore, the mixture of CF4 and N2 can be efficiently separated and purified. After separation by temperature swing adsorption (adsorption at room temperature, desorption at 60 - 100 °C), CF4 and N2 with a purity of 99.99% can be obtained.

[0078] In the present invention, unless otherwise specified, the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art. Moreover, the reagents, materials, and operation steps used herein are all widely used reagents, materials, and conventional steps in the corresponding fields.

[0079] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for storing and separating high-purity electronic special gases, characterized in that: The adsorption medium is brought into contact with the electronic special gas to achieve storage of the electronic special gas; Alternatively, the adsorption medium is brought into contact with a mixed gas containing the electronic special gas to achieve separation of the electronic special gas; The adsorption medium is composed of Co 2+ 、Zn 2+ or Fe 2+ An ordered three-dimensional microporous metal-organic framework material formed by coordination with 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) or 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole).

2. The method for storing and separating high-purity electronic special gases according to claim 1, characterized in that: The preparation method of the microporous metal organic framework is: Co 2+ , 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) and a solvent are mixed and heated at 80-160°C for 24-72h to obtain Co 2+ Microporous metal-organic framework materials; Zn 2+ , 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole) is mixed with a solvent and heated at 100-160°C for 24-72h to obtain Zn 2+ Microporous metal-organic framework materials; Fe 2+ 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is mixed with a solvent, and then an acid is added and heated at 70-120°C for 24-72h to obtain Fe 2+ Microporous metal-organic framework materials; The solvent is one or more of N,N-dimethylformamide solution, methanol, and water; The acid is one or more of hydrochloric acid, nitric acid and sulfuric acid.

3. The method for storing and separating high-purity electronic special gases according to claim 2, characterized in that: The Co 2+ In the preparation method of microporous metal organic framework materials, Co 2+ The molar ratio of Co to 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is 1 to 10:1; 2+ The dosage ratio of the solvent is 1mmol:5-20mL; The Zn 2+ In the preparation method of microporous metal organic framework material, Zn 2+ The molar ratio of Zn to 1,7-dihydrodibenzo[b,e][1,4]dioxin[2,3-d:7,8-d']bis([1,2,3]triazole) is 1 to 10:1; 2+ The dosage ratio of the solvent is 1mmol:5-20mL; The Fe 2+ In the preparation method of microporous metal organic framework materials, Fe 2+ The molar ratio of Fe to 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is 1 to 10:1; 2+ The usage ratio of solvent and acid is 1mmol:5~20mL:0.1~1mL.

4. The method for storing and separating high-purity electronic special gases according to claim 2, characterized in that: The microporous metal organic framework adjusts the pore size by exchanging metal ions or adjusting the metal cluster coordination functional groups; The Co 2+ The pore size of the microporous metal organic framework material before and after adjustment is Zn 2+ The pore size of the microporous metal organic framework material before and after adjustment is Fe 2+ The pore size of the microporous metal organic framework material before and after adjustment is 5. The method for storing and separating high-purity electronic special gases according to claim 4, characterized in that: The metal ion is Zn 2+ 、Co 2+ 、Ni 2+ , Cu 2+ , Mn 2+ Mg 2+ , Fe 2+ , Ca 2+ , Cu + , Li + Any one or more of the following; The metal cluster coordination functional group is any one or more of CH3, NH2, F, I, Br, OH, CN, COOH, and OCH3.

6. The method for storing and separating high-purity electronic special gases according to claim 4, characterized in that: The method for exchanging metal ions is as follows: immersing the microporous metal organic framework material in a metal salt solution, stirring at 25 to 90° C. for 0.25 to 12 hours, thereby obtaining a microporous metal organic framework after metal ion exchange; The metal salt in the metal salt solution is a chloride, nitrate or sulfate of the metal ion; The method for adjusting the metal cluster coordination functional group is: immersing the microporous metal organic framework material or the microporous metal organic framework after metal ion exchange in a salt solution containing metal cluster coordination functional groups, stirring at 25 to 90° C. for 0.25 to 12 hours, so as to obtain a microporous metal organic framework after adjusting the metal cluster coordination functional groups; The metal cluster coordination functional group salt in the metal cluster coordination functional group salt solution is a lithium salt, sodium salt, potassium salt or cesium salt containing the metal cluster coordination functional group; The solvent in the metal salt solution and the metal cluster coordination functional group salt solution is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, methanol, water, and dimethyl sulfoxide.

7. The method for storing and separating high-purity electronic special gases according to claim 6, characterized in that: In the metal salt solution, the ratio of the metal salt to the solvent is 2-3 mmol: 10-20 mL; In the metal cluster coordination functional group salt solution, the usage ratio of the metal cluster coordination functional group salt to the solvent is 2-3 mmol: 10-20 mL.

8. The method for storing and separating high-purity electronic special gases according to claim 4, characterized in that: The electronic special gas is SF6, NF3, C3F6, CF4, BF3, C2F6, C3F8, CHF3, CF3I, C2F5I, SiH4, Si2H6, BCl3, WF6, AsF3, ClF3, AsH3 or GeF4; The mixed gas containing electronic special gas is a binary, ternary or quaternary mixed gas.

9. The method for storing and separating high-purity electronic special gases according to claim 8, characterized in that: With the Co 2+ Microporous metal organic framework materials are used as adsorption media to separate C3F6 and C3F8 mixed gases; In exchange for Ni 2+ After Co 2+ Microporous metal organic framework materials are used as adsorption media to separate CF4 and NF3 mixed gases; In exchange for Cu + After Co 2+ Microporous metal-organic framework materials are used as adsorption media to store NF3; After adjusting F, Co 2+ Microporous metal organic framework materials are used as adsorption media to separate C2F6 and CF4 mixed gases; After adjusting OH, Zn 2+ Microporous metal-organic framework materials are used as adsorption media to store BF3; After adjusting OH, Co 2+ Microporous metal-organic framework materials are used as adsorption media to store AsH3; With the Zn 2+ Microporous metal organic framework materials are used as adsorption media to separate SF6 and N2 mixed gases; In exchange for Li + Zn 2+ Microporous metal-organic framework materials are used as adsorption media to store C3F6; With the Fe 2+ Microporous metal organic framework materials are used as adsorption media to separate CF4 and N2 mixed gases; Fe after adjusting F 2+ Microporous metal-organic framework materials are used as adsorption media to store GeF4.

10. The method for storing and separating high-purity electronic special gases according to claim 1, characterized in that: The storage method is as follows: the electronic special gas is charged into a negative pressure tank filled with a spherical, columnar, strip or block-shaped microporous metal organic framework material; the adsorption operation pressure is 0.3-1 bar, and the desorption release pressure is 0.1-0.8 bar; the storage capacity of the electronic special gas is 10-180wt%, and the desorption rate is >60%; The separation method is fluidized bed adsorption, moving bed adsorption or fixed bed adsorption; the adsorption method is temperature swing adsorption, pressure swing adsorption or temperature swing-pressure swing coupled adsorption; the operating temperature is -40 to 100°C, and the operating pressure is 0.05 to 60 bar; the purity of the electronic special gas obtained after separation is 99.99 to 99.9999%.

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