Method for adsorbing and separating high-purity gas

Abstract

The invention discloses a method for adsorbing and separating high-purity gas, which belongs to the technical field of chemical separation and comprises the following steps of: separating and purifying mixed gas or isotope by using an adsorption separation medium; the adsorption separation medium is a microporous metal organic framework material which is thermally synthesized from divalent metal salt and a ligand 1, 5-dihydrobenzo [1, 2-d: 4, 5-d '] bis ([1, 2, 3] triazole) through a solvent. The microporous metal organic framework material has a uniformly distributed microporous structure, a high specific surface area and excellent thermal stability and chemical stability, and high-selectivity separation of rare gas xenon / krypton, methane / propane / ethane, propylene / ethylene, ethane / ethylene and xenon isotopes can be realized through pressure swing / temperature swing adsorption; the adsorbent has ultrahigh adsorption and storage capacity for xenon, propane, propylene and ethane, and high-purity (greater than or equal to 99.99%) xenon, krypton, methane, ethylene and ethane and high-purity isotopes of 129Xe and 131Xe can be obtained after separation.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical separation, relates to a gas separation method, and particularly relates to a method for adsorptive separation of high-purity gases. Background Art

[0002] High-purity gases play a crucial role in numerous industries, and their purity directly affects process reliability, product performance, data accuracy, and equipment safety. Therefore, in the field of chemical separation, the preparation and separation technologies of high-purity gases occupy a core position in industrial production, environmental protection, and high-tech applications. For example, the high-purity rare gases and their isotopes separated from xenon-krypton mixtures are widely used in high-tech fields such as semiconductor manufacturing, lighting, and medical treatment; methane removes other light hydrocarbon impurities during the separation process, thereby improving the energy conversion efficiency of methane and the cycle stability during storage, becoming a core step in the natural gas purification process; in addition, the efficient separation of ethylene and ethane, propylene and ethylene is an important link in the petrochemical industry. As an important basic chemical raw material, ethylene is one of the chemical products with the largest production volume in the world, and its high-purity requirement is crucial for meeting industrial demands. However, whether it is the separation of rare gases xenon / krypton, or the separation of methane / ethane / propane, ethylene / ethane, ethylene / propylene and other olefins, or the separation of isotopes, the industrial separation and purification still generally rely on cryogenic distillation technology based on the boiling point differences of different components, which has problems such as high energy consumption, large investment, and complex processes, greatly limiting the economy and sustainability of high-purity gas preparation.

[0003] Due to its advantages such as low energy consumption, low cost, and simple operation process, the adsorption separation technology has been widely used in the field of gas separation compared with the traditional cryogenic distillation technology. Metal-organic frameworks, as a class of highly tunable porous materials, show great potential in the adsorption separation technology. However, the currently reported metal-organic frameworks still have deficiencies in terms of selectivity and adsorption capacity, and further improvement is urgently needed. For example, Chinese Patent Application CN 108993417A discloses a metal-organic framework material [M2(C6O4)3]·nH2O, which can achieve the separation of xenon and krypton, and the selectivity can reach 11.2, but the adsorption capacity for xenon is only 69.8 cm 3 / g; The NU-1107-Ag(I) metal-organic framework uses Ag(I) to enhance the framework polarizability, and the selectivity for xenon-krypton is increased to 13.4, but the adsorption capacity of Xe is only 63.0 cm 3 / g (J. Am. Chem. Soc. 2023, 145, 2679-2689); The ZUL-C1 metal-organic framework can effectively separate ethane and propane in methane, but the adsorption amounts of ethane and propane are both low, only 63.2 cm 3 / g and 60.9 cm 3 / g (J. Am. Chem. Soc. 2022, 144, 14322 - 14329); JLU - MOF132 metal - organic framework can preferentially adsorb propylene, and the separation selectivity for propylene and ethylene can reach 15.1, but the adsorption amount of propylene is only 67.5 cm 3 / g (Chem. Eng. J. 2024, 498, 155176); Cu I @UiO - 66-(COOH)2 metal - organic framework shows the characteristic of preferentially adsorbing ethylene and can effectively separate ethylene and ethane, but its ethylene adsorption capacity is only 47.9 cm 3 / g. At the same time, during the desorption process, due to a small amount of ethane impurities remaining in the adsorbent, the purity of the desorbed ethylene is relatively low, only 92.5% (Adv. Sci. 2020, 7, 1901918). In addition, there is little research on the separation of Xe isotopes. To sum up, it is urgent to develop a metal - organic framework with high adsorption amounts for xenon, ethane, propane, and propylene, which can preferentially adsorb ethane when separating the ethylene - ethane mixture and also has the effect of separating Xe isotopes. Summary of the Invention

[0004] The present invention provides a method for adsorptive separation of high - purity gases to overcome the defects of the prior art.

[0005] To achieve the above - mentioned purpose, the present invention adopts the following technical solutions:

[0006] A method for adsorptive separation of high - purity gases, which uses an adsorptive separation medium to separate a gas mixture or isotopes; the adsorptive separation medium is a microporous metal - organic framework material synthesized by solvothermal method from a divalent metal salt and a ligand 1,5 - dihydrobenzo[1,2 - d:4,5 - d']bis([1,2,3]triazole).

[0007] Among them, the structural formula of 1,5 - dihydrobenzo[1,2 - d:4,5 - d']bis([1,2,3]triazole) is:

[0008] To optimize the above - mentioned technical solution, the specific measures taken further include:

[0009] Further, the divalent metal salt is any one of nitrates, chlorides, and sulfates of Cu, Co, Mn, and Fe; the molar ratio of the divalent metal salt to 1,5 - dihydrobenzo[1,2 - d:4,5 - d']bis([1,2,3]triazole) is 1 - 10:1.

[0010] Further, the pore size of the microporous metal - organic framework material is 0.4 - 1.0 nm, and the BET specific surface area is 1000 - 1800 m 2 / g.

[0011] Further, the preparation method of the microporous metal-organic framework material is as follows: A divalent metal salt and 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) are added to a solvent, and the reaction is carried out at 80-160 °C for 24-72 h to obtain the microporous metal-organic framework material.

[0012] Further, the solvent is any one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and methanol; the dosage ratio of the solvent to the divalent metal salt is 2-15 mL∶1 mmol.

[0013] Further, the method for separating a mixed gas by the microporous metal-organic framework material is as follows: contacting with the mixed gas, adsorbing one or more gases in the mixed gas to separate it from the remaining gas, and obtaining a high-purity gas by collecting the gas downstream of the adsorption or desorbing the gas; the method for separating isotopes by the microporous metal-organic framework material is as follows: contacting with a mixed isotope, adsorbing one or more isotopes in the mixed isotope to separate it from the remaining isotopes.

[0014] Further, the separation method is fluidized bed adsorption, moving bed adsorption, fixed bed adsorption or micro-packed bed adsorption; the adsorption method is temperature swing adsorption, pressure swing adsorption or pressure-temperature swing coupling adsorption; the operating temperature for separating the mixed gas is 0-100 °C, and the operating pressure is 0.05-10 bar. Preferably, adsorption is carried out at normal temperature and pressure, and desorption is carried out at 60-100 °C or 0.05-0.1 bar; the operating temperature for separating isotopes is -100-100 °C, and the operating pressure is 1-10 bar. Preferably, adsorption is carried out at -100--75 °C and normal pressure, and desorption is carried out at 40-100 °C or 0.05-0.1 bar.

[0015] Further, the mixed gas is a mixed gas of xenon and krypton, a mixed gas of methane, ethane and propane, a mixed gas of ethane and ethylene, a mixed gas of ethylene and propylene, or a mixed gas of methane, ethane, ethylene, propylene and propane; the purity of the single-component gas obtained after separation is ≥99.99%; the isotope is xenon isotope, and the separated isotope species are 129 Xe, 131 Xe. After separation, the isotope abundance is ≥98.0% and the purity is ≥99%.

[0016] Further, in the xenon and krypton gas mixture, the volume ratio of xenon to krypton is 1-50:50-99; in the methane, ethane and propane gas mixture, the volume ratio of methane, ethane and propane is 1-10:1-5:85-98; in the ethane and ethylene gas mixture, the volume ratio of ethane to ethylene is 1-50:50-99; in the ethylene and propylene gas mixture, the volume ratio of ethylene to propylene is 1-50:50-99; in the methane, ethane, ethylene, propylene and propane gas mixture, the volume ratio of methane, ethane, ethylene, propylene and propane is 1-20:1-20:1-35:1-20:1-5.

[0017] Further, a microporous metal-organic framework material synthesized from cobalt nitrate is used as an adsorption separation medium for separating a xenon and krypton gas mixture; after the microporous metal-organic framework material contacts the xenon and krypton gas mixture, xenon is preferentially adsorbed, and the purity of the recovered xenon and krypton is as high as over 99.999%; a microporous metal-organic framework material synthesized from copper chloride is used as an adsorption separation medium for separating a methane, ethane and propane gas mixture; (after the microporous metal-organic framework material contacts the methane, ethane and propane gas mixture, ethane and propane are preferentially adsorbed, and the purity of the recovered methane is as high as over 99.99%; a microporous metal-organic framework material synthesized from copper sulfate is used as an adsorption separation medium for separating an ethane and ethylene gas mixture; after the microporous metal-organic framework material contacts the ethane and ethylene gas mixture, ethane is preferentially adsorbed, and the purity of the recovered ethylene is as high as over 99.99%; a microporous metal-organic framework material synthesized from iron chloride is used as an adsorption separation medium for separating an ethylene and propylene gas mixture; after the microporous metal-organic framework material contacts the ethylene and propylene gas mixture, propylene is preferentially adsorbed, and the purity of the recovered ethylene and propylene is as high as over 99.99%; a microporous metal-organic framework material synthesized from copper nitrate is used as an adsorption separation medium for a methane, ethane, ethylene, propylene and propane gas mixture; after the microporous metal-organic framework material contacts the methane, ethane, ethylene, propylene and propane gas mixture, propylene, propane, ethane and ethylene are preferentially adsorbed, and the purity of the recovered methane is as high as over 99.99%; a microporous metal-organic framework material synthesized from cobalt chloride is used as an adsorption separation medium for separating xenon isotopes 129 Xe and 131 Xe; after the microporous metal-organic framework material contacts xenon at low temperature, the more abundant and heavier 129 Xe and 131 Xe are preferentially adsorbed. After desorption, further separation of the 129 Xe and 131 Xe mixed isotopes is carried out at low temperature to obtain high-abundance 129 Xe, 131 Xe.

[0018] The beneficial effects of the present invention are as follows:

[0019] 1. The adsorption separation medium used in the separation method of the present invention is a microporous metal-organic framework material synthesized by solvothermal method from divalent metal salt and ligand 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole). While having high selectivity, this adsorption separation medium also has high adsorption capacity for xenon, propane, and ethane, far superior to most other solid adsorbents. When separating the mixture of ethane and ethylene, this adsorption separation medium can preferentially adsorb ethane without desorption, thus obtaining high-purity ethylene in one step. At the same time, this adsorption separation medium can efficiently separate xenon isotopes.

[0020] Specifically, the microporous metal-organic framework material of this application is a cubic MOF with Kuratowski structure, having a uniformly distributed pore structure and a high specific surface area, which provides strong support for high adsorption capacity, thus showing excellent performance in terms of separation selectivity and adsorption capacity. In addition, the pore diameter of this microporous metal-organic framework material is between 0.4 - 1.0 nm, matching the kinetic diameters (0.41 - 0.52 nm) of the preferentially adsorbed guest molecules. Therefore, the abundant hydrogen and nitrogen atoms on the ligand and the metal cluster functional groups can form strong electrostatic interactions and hydrogen bonds and other physical adsorption forces with the preferentially adsorbed guest molecules, thus significantly enhancing the adsorption selectivity.

[0021] 2. The microporous metal-organic framework material, which is the adsorption separation medium used in the separation method of the present invention, is easy to regenerate, has high structural stability and long service life, and its preparation method has the advantages of simple synthesis method, mild conditions, easy batch preparation, etc., and has good industrial application prospects.

[0022] 3. Compared with the traditional cryogenic distillation technology, the separation method provided by the present invention has the advantages of low energy consumption, simple operation, and small equipment investment. Description of the Drawings

[0023] Figure 1 is the adsorption isotherm diagram of the microporous metal-organic framework material in Example 1 for N2 at 77K;

[0024] Figure 2 is the adsorption isotherm diagram of the microporous metal-organic framework material in Example 2 for xenon and krypton at 298K;

[0025] Figure 3 is the adsorption isotherm diagram of the microporous metal-organic framework material in Example 3 for methane, ethane, and propane at 298K;

[0026] Figure 4 is the adsorption isotherm diagram of the microporous metal-organic framework material in Example 4 for ethane and ethylene at 298K;

[0027] Figure 5It is the adsorption isotherm diagram of the microporous metal-organic framework material in Example 5 for ethylene and propylene at 298K;

[0028] Figure 6 It is for the microporous metal-organic framework material in Example 7 at 173K for 129 Xe and 131 the adsorption isotherm diagram of Xe. Specific Embodiments

[0029] The present invention will be further described below in conjunction with specific embodiments.

[0030] Example 1

[0031] This example provides a method for adsorptive separation of high-purity gases: using a microporous metal-organic framework material as an adsorptive separation medium to separate a mixed gas.

[0032] The preparation method of the microporous metal-organic framework material is as follows: Place 0.5 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a culture flask, add 8 mL of N,N-dimethylformamide, after dissolution, add 1 mmol of manganese chloride, stir for 5 min, and then react at 110 °C for 36 h to obtain the microporous metal-organic framework material.

[0033] After activating the microporous metal-organic framework material obtained in this example, the N2 adsorption-desorption curve was measured at 77K, and the results are as Figure 1 shown, and its BET specific surface area is 1619.7 m 2 / g.

[0034] Example 2

[0035] This example provides a method for adsorptive separation of high-purity gases: using a microporous metal-organic framework material as an adsorptive separation medium to separate a mixed gas.

[0036] The preparation method of the microporous metal-organic framework material is as follows: Place 1 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene liner, add 15 mL of N,N-dimethylformamide, after dissolution, add 2 mmol of cobalt nitrate, stir for 5 min, and then react at 140 °C for 48 h to obtain the microporous metal-organic framework material.

[0037] The adsorption behavior of the activated microporous metal-organic framework material in this example for xenon and krypton was measured at 298K, and its adsorption isotherm is as Figure 2 shown. The adsorption amount of the microporous metal-organic framework material for xenon is 139.3 cm 3 / g, and the adsorption amount for krypton is only 28.6 cm 3 / g. Therefore, the microporous metal-organic framework material can efficiently separate and purify the mixture of xenon and krypton. After separation by pressure swing adsorption (adsorption at atmospheric pressure and desorption at 0.05 - 0.1 bar), xenon and krypton with a purity of 99.999% can be obtained.

[0038] Example 3

[0039] This example provides a method for the adsorption separation of high-purity gases: using a microporous metal-organic framework material as the adsorption separation medium to separate the mixed gas.

[0040] The preparation method of the microporous metal-organic framework material is as follows: Place 1 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add a mixed solution of 5 mL of methanol and 5 mL of N,N-dimethylformamide. After dissolution, add 4 mmol of copper chloride, stir for 5 min, and then react at 150 °C for 48 h to obtain the microporous metal-organic framework material.

[0041] At 298 K, the adsorption behavior of the activated microporous metal-organic framework material in this example for methane, ethane, and propane was tested, and its adsorption isotherm is as Figure 3 shown. The adsorption amounts of the microporous metal-organic framework material for ethane and propane are 134.7 cm 3 / g and 121.1 cm 3 / g respectively, and the adsorption amount for methane is only 22.5 cm3 / g. Therefore, the microporous metal-organic framework material can efficiently separate and purify the mixture of methane, ethane, and propane. After separation by temperature swing adsorption (adsorption at room temperature and desorption at 60 - 100 °C), methane with a purity of 99.99% can be obtained.

[0042] Example 4

[0043] This example provides a method for the adsorption separation of high-purity gases: using a microporous metal-organic framework material as the adsorption separation medium to separate the mixed gas.

[0044] The preparation method of the microporous metal-organic framework material is as follows: Place 0.5 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add 15 mL of N,N-dimethylacetamide. After dissolution, add 3 mmol of copper sulfate, stir for 5 min, and then react at 140 °C for 72 h to obtain the microporous metal-organic framework material.

[0045] At 298 K, the adsorption behavior of the activated microporous metal-organic framework material in this example for ethane and ethylene was tested, and its adsorption isotherm is as Figure 4 shown. The adsorption amount of the microporous metal-organic framework material for ethane is 135.8 cm 3 / g, greater than 125.9 cm of ethylene 3 / g. Therefore, the microporous metal-organic framework material can efficiently separate and purify the ethane and ethylene mixture. After separation by temperature swing adsorption (adsorption at room temperature and desorption at 60 - 100 °C), ethane and ethylene with a purity of 99.99% can be obtained.

[0046] Example 5

[0047] This example provides a method for the adsorption separation of high-purity gases: using a microporous metal-organic framework material as the adsorption separation medium to separate the mixed gas.

[0048] The preparation method of the microporous metal-organic framework material is as follows: Place 0.75 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add 15 mL of N,N-dimethylacetamide. After dissolution, add 3 mmol of ferric chloride, stir for 5 min, and then react at 140 °C for 48 h to obtain the microporous metal-organic framework material.

[0049] At 298 K, the adsorption behavior of the activated microporous metal-organic framework material in this example for ethylene and propylene was tested, and its adsorption isotherm is as Figure 5 shown. The adsorption capacity of the microporous metal-organic framework material for propylene is 154.2 cm 3 / g, and the adsorption capacity for ethylene is 135.4 cm 3 / g. Therefore, the microporous metal-organic framework material can efficiently separate and purify the ethylene and propylene mixture. After separation by temperature swing adsorption (adsorption at room temperature and desorption at 60 - 100 °C), ethylene and propylene with a purity of 99.99% can be obtained.

[0050] Example 6

[0051] This example provides a method for the adsorption separation of high-purity gases: using a microporous metal-organic framework material as the adsorption separation medium to separate the mixed gas.

[0052] The preparation method of the microporous metal-organic framework material is as follows: Place 1 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) in a polytetrafluoroethylene inner liner, add a mixed solution of 10 mL of methanol and 5 mL of N,N-dimethylformamide. After dissolution, add 2 mmol of cobalt chloride, stir for 5 min, and then react at 130 °C for 48 h to obtain the microporous metal-organic framework material.

[0053] Example 7

[0054] This example provides a method for the adsorption separation of high-purity gases: using a microporous metal-organic framework material as the adsorption separation medium to separate xenon isotopes.

[0055] The preparation method of the microporous metal-organic framework material is as follows: 0.75 mmol of 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is placed in a polytetrafluoroethylene inner liner, 15 mL of N,N-dimethylacetamide is added, and after dissolution, 3 mmol of cobalt chloride is added. After stirring for 5 min, the reaction is carried out at 140 °C for 48 h to obtain the microporous metal-organic framework material.

[0056] The adsorption behavior of the activated microporous metal-organic framework material of this example for Xe isotopes was tested at 173 K, and its adsorption for 129 Xe, 131 The Xe adsorption isotherm is as shown in Figure 6 the figure. The adsorption amount of the microporous metal-organic framework material for 131 Xe is 122.5 cm 3 / g, and the adsorption amount for 129 Xe is 116.2 cm 3 / g. Therefore, the microporous metal-organic framework material can efficiently separate and purify Xe isotopes. By using temperature swing adsorption (adsorbing pure Xe at 198 K, preferentially adsorbing 129 Xe and 131 Xe in pure Xe, desorbing at 60 - 100 °C; then adsorbing the 129 Xe and 131 Xe after desorption at 173 K, preferentially adsorbing 131 Xe, obtaining the remaining 129 Xe, and then desorbing at 60 - 100 °C to obtain 131 Xe), after separation, Xe with an abundance of 98.0% and a purity of 99.0% can be obtained. 129 Xe, 131 Xe.

[0057] 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. And the reagents, materials, and operation steps used herein are all widely used reagents, materials, and conventional steps in the corresponding fields.

[0058] 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 recorded 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 principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for separation of high-purity gas by adsorption, characterized in that: Separation of mixed gases or isotopes using adsorption separation media; The adsorption separation medium is a microporous metal organic framework material synthesized by solvent thermal synthesis from a divalent metal salt and a ligand 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole).

2. The method for high-purity gas adsorption separation according to claim 1, characterized in that: The divalent metal salt is any one of nitrate, chloride and sulfate of Cu, Co, Mn and Fe; The molar ratio of the divalent metal salt to 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) is 1 to 10:

1.

3. The method for high-purity gas adsorption separation according to claim 1, characterized in that: The pore size of the microporous metal organic framework material is 0.4-1.0 nm, and the BET specific surface area is 1000-1800 m 2 / g.

4. The method for high-purity gas adsorption separation according to claim 1, characterized in that: The preparation method of the microporous metal organic framework material is: adding a divalent metal salt and 1,5-dihydrobenzo[1,2-d:4,5-d']bis([1,2,3]triazole) into a solvent, reacting at 80-160° C. for 24-72 hours to obtain the microporous metal organic framework material.

5. The method for high-purity gas adsorption separation according to claim 4, characterized in that: The solvent is any one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and methanol; The usage ratio of the solvent to the divalent metal salt is 2-15 mL: 1 mmol.

6. The method for separation of high-purity gas by adsorption according to claim 1, characterized in that: The method for separating the mixed gas by the microporous metal organic framework material is: contacting with the mixed gas, adsorbing one or more gases in the mixed gas to separate it from the remaining gas, and obtaining high-purity gas by collecting the adsorbed downstream gas or the desorbed gas; The method for separating isotopes of the microporous metal organic framework material is: contacting with mixed isotopes, adsorbing one or more isotopes in the mixed isotopes, and separating them from the remaining isotopes.

7. The method for separation of high-purity gas by adsorption according to claim 1, characterized in that: The separation method is fluidized bed adsorption, moving bed adsorption, fixed bed adsorption or micro-packed bed adsorption; The adsorption method is temperature swing adsorption, pressure swing adsorption or pressure swing-temperature swing coupled adsorption; the operating temperature for separating the mixed gas is 0-100°C, and the operating pressure is 0.05-10 bar; the operating temperature for separating the isotopes is -100-100°C, and the operating pressure is 1-10 bar.

8. The method for separation of high-purity gas by adsorption according to claim 1, characterized in that: The mixed gas is a mixed gas of xenon and krypton, a mixed gas of methane, ethane and propane, a mixed gas of ethane and ethylene, a mixed gas of ethylene and propylene, or a mixed gas of methane, ethane, ethylene, propylene and propane; the purity of the single-component gas obtained after separation is ≥99.99%; The isotope is a xenon isotope, and the separated isotope species are 129 Xe, 131 Xe, after separation, has an isotopic abundance of ≥98.0% and a purity of ≥99%.

9. The method for high-purity gas adsorption separation according to claim 8, characterized in that: In the xenon and krypton gas mixture, the volume ratio of xenon gas to krypton gas is 1-50:50-99; In the methane, ethane and propane mixed gas, the volume ratio of methane, ethane and propane is 1-10:1-5:85-98; In the ethane and ethylene mixed gas, the volume ratio of ethane to ethylene is 1-50:50-99; In the ethylene and propylene mixed gas, the volume ratio of ethylene to propylene is 1-50:50-99; In the mixed gas of methane, ethane, ethylene, propylene and propane, the volume ratio of methane, ethane, ethylene, propylene and propane is 1-20:1-20:1-35:1-20:1-5.

10. The method for separation of high-purity gas by adsorption according to claim 8, characterized in that: A microporous metal organic framework material synthesized from cobalt nitrate was used as an adsorption separation medium to separate a mixture of xenon and krypton. A microporous metal organic framework material synthesized from cupric chloride was used as an adsorption separation medium to separate a mixture of methane, ethane and propane; A microporous metal organic framework material synthesized from copper sulfate was used as an adsorption separation medium to separate ethane and ethylene mixed gases; A microporous metal organic framework material synthesized from ferric chloride was used as an adsorption separation medium to separate ethylene and propylene mixed gases; Using microporous metal organic framework materials synthesized from copper nitrate as adsorption separation media, methane, ethane, ethylene, propylene and propane mixed gases; Microporous metal-organic frameworks synthesized from cobalt chloride as adsorption separation media for separation of xenon isotopes 129 Xe and 131 Xe.

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