CN110237816B - Preparation method and application of silver nitrate-modified metal organic framework adsorption material - Google Patents

Preparation method and application of silver nitrate-modified metal organic framework adsorption material Download PDF

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CN110237816B
CN110237816B CN201910512978.9A CN201910512978A CN110237816B CN 110237816 B CN110237816 B CN 110237816B CN 201910512978 A CN201910512978 A CN 201910512978A CN 110237816 B CN110237816 B CN 110237816B
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silver nitrate
ethylene
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张壮壮
殷俞
袁爱华
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Jiangsu University of Science and Technology
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Abstract

The invention discloses a preparation method of a silver nitrate-modified metal organic framework adsorption material, which comprises the following steps: dropwise adding a silver nitrate solution into n-hexane dispersed with a metal organic framework, fully mixing, and then placing the mixture in an inert atmosphere to carry out heat treatment at a temperature of not higher than 105 ℃ to obtain the silver nitrate modified metal organic framework adsorbing material. The active metal sites Ag (I) in the adsorbing material prepared by the preparation method have good dispersibility on a metal organic framework, so that the separation selectivity of the silver nitrate modified metal organic framework adsorbing material in the process of adsorbing and separating ethylene/ethane is effectively improved.

Description

Preparation method and application of silver nitrate-modified metal organic framework adsorption material
Technical Field
The invention relates to a preparation method of a silver nitrate-modified metal organic framework adsorbing material, and also relates to application of the adsorbing material prepared by the preparation method in the aspect of adsorbing and separating ethylene/ethane, belonging to the technical field of chemical materials.
Background
Ethylene is used as a raw material for synthesizing products such as detergents, medicines, dyes and the like, and has great demand in the fine chemical fields such as petrochemical industry, light chemical industry, pharmaceutical industry and the like, and the ethylene yield and the ethylene development technology mark the development level of the national petrochemical industry. In recent years, the annual growth rate of global ethylene production has been maintained at 4% to 5% (world reforming Business Digest Weekly, 2009.11.16). At present, ethylene and ethane are mainly industrially derived from catalytic cracking of petroleum, the catalytic cracking of petroleum is a complex process accompanied by the generation of various impurities, and the ethylene is obtained by separating and purifying from an ethylene and ethane gas mixture generated by cracking of petroleum. Due to the similar relative volatility and molecular structure size of the two components to be separated, the separation of ethylene/ethane is difficult to achieve by conventional methods. At present, the most extensive separation method adopts a low-temperature rectification method, the temperature required by the method is as low as-25 ℃, the pressure is higher than 2.0MPa, and the operation conditions are extremely harsh. According to the statistics of the U.S. department of energy, the energy consumed in the low-temperature rectification separation of olefin/alkane in the United states is 3.024 multiplied by 1015cal is equivalent to eachAnnual consumption of 1.0X 107Ten thousand tons of standard coal (u.s.department of Energy Report, 1991, 12920-. Based on the need for energy saving and consumption reduction, there is an urgent need to develop new processes for ethylene/ethane separation.
The pi-complex adsorption separation technology can effectively separate ethylene/ethane mixed gas at normal temperature, and is known as one of the most potential technologies for replacing low-temperature rectification. The principle of complex adsorption is that the ethylene/ethane gas mixture is contacted with the adsorption material containing transition metal, and because the transition metal and ethylene form pi complex bond, the pi complex bond and ethane are only van der waals force, and the purpose of separating ethylene/ethane is realized by utilizing the bond energy of the complex bond which is stronger than van der waals force. Ag (i) is one of the most effective pi-complex adsorption active metal sites. However, at present, such materials face the problem of poor dispersion of ag (i) on the support, so that further improvements in adsorption capacity and separation selectivity remain a challenge.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a preparation method of a silver nitrate modified metal organic framework adsorption material, wherein active metal sites Ag (I) in the adsorption material prepared by the preparation method have good dispersibility (uniform dispersion) on a metal organic framework, so that the separation selectivity of the silver nitrate modified metal organic framework adsorption material in the process of adsorbing and separating ethylene/ethane is effectively improved.
The invention content is as follows: in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a silver nitrate-modified metal organic framework adsorption material comprises the following steps: dropwise adding a silver nitrate solution into n-hexane dispersed with a metal organic framework, fully mixing, and then placing the mixture in an inert atmosphere to carry out heat treatment at a temperature of not higher than 105 ℃ to obtain the silver nitrate modified metal organic framework adsorbing material.
Wherein the heat treatment temperature is 100-105 ℃, and the heat treatment time is 1-12 hours.
Wherein the inert gas atmosphere is one of high-purity argon, high-purity nitrogen or high-purity helium.
Wherein the type of the metal organic framework is one of MIL-101, ZIF-8 or HKUST-1.
Wherein, in the mixed material, the mixing mass ratio of the silver nitrate to the metal organic framework material is 0.4-2.
The metal organic framework material is uniformly dispersed in a hydrophobic solvent n-hexane, and due to the hydrophobicity of the n-hexane, a hydrophilic silver nitrate solution can enter the inside of a pore channel of the metal organic framework material, so that silver nitrate can be highly dispersed in the pore channel of the metal organic framework carrier, and the pi-complex adsorption material capable of efficiently separating ethylene/ethane is obtained. The preparation method realizes the high dispersion of silver nitrate on the metal organic framework material, the silver nitrate and C-C double bonds in ethylene form pi complex bonds, the bonds of the pi complex bonds can be stronger than Van der Waals force, and simultaneously, the adsorption capacity of the adsorption material to ethylene is higher than that of ethane, thereby realizing the separation of ethylene/ethane.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the preparation method can effectively improve the dispersion degree of the silver nitrate on the metal organic framework carrier, so that more adsorption materials which can contact with active metal sites are obtained, and the separation selectivity of the adsorption materials on ethylene/ethane is improved; in addition, the preparation method is simple and easy to implement, is easy to realize, and has good application prospect.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the adsorbent material prepared by the three methods.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific examples.
The adsorbing material takes a metal organic framework as a carrier, and silver nitrate is modified on the carrier to obtain the silver nitrate-loaded metal organic framework adsorbing material. The process of modifying silver nitrate on the carrier is a double-solvent method, the carrier is dispersed in a hydrophobic n-hexane solvent, so that a hydrophilic silver nitrate solution enters the inside of a pore channel of the carrier to realize high dispersion of the silver nitrate on the carrier,
example 1
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 0.2857g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption capacity of the adsorbent for ethylene at 100kPa was 58.3cm3g-1The adsorption amount of ethane was 36.2cm3g-1。
Example 2
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 0.4285g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption capacity of the adsorbent for ethylene at 100kPa was 60.5cm3g-1Adsorption of ethaneThe amount was 34.3cm3g-1。
Example 3
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 0.5714g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 62.4cm3g-1The adsorption amount of ethane was 32.5cm3g-1。
Example 4
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 0.7142g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 63.6cm3g-1Adsorption amount of ethaneIs 26.5cm3g-1。
Example 5
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 0.8571g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 64.5cm3g-1The adsorbed amount of ethane was 23.9cm3g-1。
Example 6
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.0g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 66.1cm3g-1And an adsorbed amount of ethane of 19.0cm3g-1。
Example 7
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.1428g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 75.5cm3g-1The adsorption amount of ethane was 17.3cm3g-1。
Example 8
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.2857g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 68.4cm3g-1And an adsorbed amount of ethane of 16.8cm3g-1。
Example 9
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.4285g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 64.7cm3g-1The adsorption amount of ethane was 16.6cm3g-1。
Example 10
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated in a vacuum drying oven for 12 hours at 150 ℃, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15 minutes, then stirring for 2 hours to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.1428g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2 hours, then filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2 hours, and carrying out heat treatment on the dried sample at 105 ℃ for 12 hours under a high-purity helium atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 74.3cm3g-1And an adsorbed amount of ethane of 18.2cm3g-1。
Example 11
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.1428g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity nitrogen atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 72.6cm3g-1And an adsorbed amount of ethane of 19.5cm3g-1。
Example 12
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.1428g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 6h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption capacity of the adsorbent for ethylene at 100kPa was 71.8cm3g-1And an adsorbed amount of ethane of 19.8cm3g-1。
Example 13
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.1428g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 4h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 71.2cm3g-1The adsorption amount of ethane was 20.4cm3g-1。
Example 14
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 140uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.1428g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 1h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 69.3cm3g-1The adsorption amount of ethane was 21.5cm3g-1。
Example 15
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 which is activated for 12 hours at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15 minutes, then stirring for 2 hours to obtain an n-hexane solution dispersed with the metal organic framework, adding 60uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.1428g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2 hours, then filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2 hours, and carrying out heat treatment on the dried sample at 105 ℃ for 12 hours under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 38.4cm3g-1The adsorbed amount of ethane was 23.3cm3g-1。
Example 16
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 activated for 12h at 150 ℃ in a vacuum drying oven, adding the metal organic framework MIL-101 into 20mL of n-hexane, carrying out ultrasonic treatment for 15min, then stirring for 2h to obtain an n-hexane solution dispersed with the metal organic framework, adding 50uL of silver nitrate solution (the silver nitrate solution is prepared by dissolving 1.1428g of silver nitrate in 1mL of water) into the n-hexane solution dispersed with the metal organic framework by using a microsyringe, stirring the mixed solution for 2h, filtering, drying the filtered sample at 40 ℃ in the vacuum drying oven for 2h, and carrying out heat treatment on the dried sample at 105 ℃ for 12h under a high-purity argon atmosphere.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 34.7cm3g-1The adsorbed amount of ethane was 25.6cm3g-1。
Comparative example 1
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.1g of metal organic framework MIL-101 and 0.16g of silver nitrate which are activated for 12 hours in a vacuum drying oven at 150 ℃, fully mixing, grinding for 30min at room temperature, and carrying out heat treatment on the mixed material for 12 hours at 105 ℃ under the atmosphere of high-purity argon after grinding.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 19.4cm3g-1The adsorbed amount of ethane was 13.9cm3g-1。
Comparative example 2
Preparing a silver nitrate modified metal organic framework adsorption material: weighing 0.16g of silver nitrate in a beaker, adding 10mL of water, and stirring to fully dissolve the silver nitrate to obtain a silver nitrate solution; weighing 0.1g of MIL-101 activated in a vacuum drying oven at 150 ℃ for 12 hours, adding the MIL-101 into a silver nitrate solution, heating the mixture in a water bath at 50 ℃, taking out a sample after water is completely evaporated, and carrying out heat treatment on the sample at 105 ℃ for 12 hours under the atmosphere of high-purity argon.
Adsorption capacity of the test material for ethylene/ethane: the adsorption capacity of the adsorption material on ethylene/ethane is tested by adopting Belsorp max; the test condition of the adsorbing material is 25 ℃, and the pressure range is 0-100 kPa. The adsorption amount of the adsorbent to ethylene at 100kPa was 56.1cm3g-1The adsorbed amount of ethane was 17.9cm3g-1。
According to the embodiments 1-9, different silver nitrate introduction amounts have great influence on the adsorption separation selectivity of the final adsorption material, and when the silver nitrate introduction amount is 1.1428g, the adsorption separation selectivity of the adsorption material on ethylene/ethane is the best; it is clear from examples 7, 10 and 11 that the selection of the inert atmosphere has little effect on the performance of the adsorbent; it is understood from examples 7, 12, 13 and 14 that the heat treatment time does not greatly affect the performance of the adsorbent; it is understood from examples 7, 15 and 16 that when the amount of silver nitrate introduced is 1.1428g, the volume of the silver nitrate solution added to the n-hexane solution in which the metal-organic framework is dispersed has a great influence on the adsorptive separation selectivity of the adsorbent.
Compared with the metal organic framework adsorbing material loaded with Ag (I) in the prior art, on one hand, the adsorbing capacity of the metal organic framework adsorbing material to ethylene is low and is 20cm3g-1On the other hand, the separation selectivity of the adsorbent to ethylene/ethane is low, generally 14.2-21.3, and the adsorption quantity and the separation selectivity are far lower than those of the metal organic framework adsorbent material prepared by the method.
As shown in FIG. 1, example 7 is an adsorbent prepared by the two-solvent method, and AgNO is not shown on the spectrum3Characteristic peak of (a); the adsorption material prepared by grinding or dipping method has strong AgNO on the map3Diffraction peaks. Thus, AgNO in the two-solvent method3A high degree of dispersion is achieved.

Claims (5)

1. A preparation method of a silver nitrate modified metal organic framework adsorption material is characterized by comprising the following steps: the method specifically comprises the following steps: dropwise adding a silver nitrate aqueous solution into n-hexane dispersed with a metal organic framework, fully mixing, and then placing the mixture in an inert atmosphere for heat treatment at a temperature of not higher than 105 ℃ to obtain a silver nitrate modified metal organic framework adsorbing material; the heat treatment temperature is 100-105 ℃, and the heat treatment time is 1-12 hours; the inert atmosphere is one of high-purity argon, high-purity nitrogen or high-purity helium.
2. The method for preparing a silver nitrate-modified metal organic framework adsorbing material according to claim 1, which is characterized in that: the type of the metal organic framework is one of MIL-101, ZIF-8 or HKUST-1.
3. The method for preparing a silver nitrate-modified metal organic framework adsorbing material according to claim 1, which is characterized in that: in the mixed material, the mixing mass ratio of silver nitrate to the metal organic framework material is 0.4-2: 1.
4. the use of the adsorption material prepared by the method for preparing a silver nitrate-modified metal organic framework adsorption material according to claim 1 for the adsorptive separation of ethylene/ethane.
5. The application of the adsorption material prepared by the preparation method of the silver nitrate-modified metal organic framework adsorption material in the aspect of adsorption separation of ethylene/ethane according to claim 4 is characterized in that: the using conditions of the adsorbing material are as follows: adsorbing the ethylene/ethane mixed gas at 25 ℃ under a pressure ranging from 0 to 100 kPa.
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