CN110237816A - A kind of preparation method and applications of the metal organic framework adsorbent material of nitric acid modified by silver - Google Patents
A kind of preparation method and applications of the metal organic framework adsorbent material of nitric acid modified by silver Download PDFInfo
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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Abstract
The invention discloses a kind of preparation methods of the metal organic framework adsorbent material of nitric acid modified by silver, this method specifically: silver nitrate solution is added dropwise in the n-hexane for being dispersed with metal organic framework, mixed material is placed in inert atmosphere at a temperature of not higher than 105 DEG C after being sufficiently mixed and is heat-treated, the metal organic framework adsorbent material of nitric acid modified by silver is obtained.Active metal sites Ag (I) in adsorbent material made from the preparation method has good dispersibility on metal organic framework, to effectively improve separation selectivity of the metal organic framework adsorbent material of nitric acid modified by silver in adsorbing separation ethylene/ethane.
Description
Technical field
The present invention relates to a kind of preparation method of the metal organic framework adsorbent material of nitric acid modified by silver, the invention further relates to
Application of the adsorbent material made from above-mentioned preparation method in terms of adsorbing separation ethylene/ethane, belongs to chemical material technical field.
Background technique
Raw material of the ethylene as some products such as synthetic detergent, medicine, dyestuff, in petro chemical industry, light industry industry
There is very big demand with field of fine chemical such as pharmaceutical sectors, the yield of ethylene and the development technique of ethylene indicate a national stone
The development level of oiling work.In recent years, the yield annual growth of global ethylene maintains 4%~5% (Worldwide
Refining Business Digest Weekly, 2009.11.16).Currently, industrial ethylene and ethane are mainly derived from stone
The catalytic pyrolysis of oil, petroleum catalytic pyrolysis are a complicated processes, can be with the generation of various impurity, and the preparation method of ethylene
It is to isolate and purify to obtain from the ethylene and ethane gas mixture that petroleum cracking generates.Since bi-component to be separated is with close
Relative volatility and molecular structure size, common method be difficult to realize ethylene/ethane separation.Currently, widest point
It is to use cryogenic rectification method from method, for temperature needed for this method down to -25 DEG C, pressure is higher than 2.0MPa, and operating condition is extremely severe
It carves.Counted according to U.S. Department of Energy, entire United States every year the energy that consumes in the separation of olefin/paraffin cryogenic rectification be 3.024 ×
1015Cal is equivalent to annual consumption 1.0 × 107Ten thousand tons of standard coals (U.S.Department of Energy Report, 1991,
12920-12921), it is also considered as one of the industrial process to consume energy the most.Based on energy-saving demand, there is an urgent need to develop
New method is used for the separation of ethylene/ethane.
π Absorptive complex wave isolation technics can efficiently separate ethylene/ethane mixed gas at normal temperature, be known as most having latent
One of the technology of power substitution cryogenic rectification.The principle of Absorptive complex wave is by ethylene/ethane admixture of gas and to contain transition metal
Adsorbent material contact be only Van der Waals force with ethane, utilize complex bonds since transition metal and ethylene form π complex bonds
Bond energy is better than Van der Waals force, realizes the purpose of separation ethylene/ethane.Ag (I) is most effective π Absorptive complex wave active metal sites
One of.However, this kind of material faces Ag (I) the bad dispersibility on carrier the problem of at present, so that further increasing adsorption capacity
It is still a challenge with separation selectivity.
Summary of the invention
Goal of the invention: technical problem to be solved by the invention is to provide a kind of suctions of the metal organic framework of nitric acid modified by silver
The preparation method of enclosure material, the active metal sites Ag (I) in adsorbent material made from the preparation method is in metal organic framework
It is upper that there is good dispersed (being uniformly dispersed), so that the metal organic framework adsorbent material for effectively improving nitric acid modified by silver is being inhaled
Separation selectivity when Fufen is from ethylene/ethane.
Summary of the invention: in order to solve the above technical problems, the technical scheme adopted by the invention is as follows:
A kind of preparation method of the metal organic framework adsorbent material of nitric acid modified by silver, this method specifically: by silver nitrate
Solution is added dropwise in the n-hexane for being dispersed with metal organic framework, and mixed material is placed in inert atmosphere after being sufficiently mixed
It is heat-treated at a temperature of not higher than 105 DEG C, obtains the metal organic framework adsorbent material of nitric acid modified by silver.
Wherein, the temperature of heat treatment is 100 DEG C~105 DEG C, and heat treatment time is 1~12 hour.
Wherein, atmosphere of inert gases is one of high-purity argon gas, high pure nitrogen or high-purity helium.
Wherein, one of model MIL-101, ZIF-8 of the metal organic framework or HKUST-1.
Wherein, in mixed material, the mixing mass ratio of silver nitrate and metal-organic framework materials is 0.4~2.
Metal-organic framework materials are homogeneously dispersed in hydrophobic solvent n-hexane, due to the hydrophobicity of n-hexane,
Hydrophilic silver nitrate solution can enter inside the duct of metal-organic framework materials, so that silver nitrate can be highly dispersed at metal
In the duct of organic backbone carrier, the π Absorptive complex wave material that can efficiently separate ethylene/ethane is obtained.Preparation method of the present invention
High degree of dispersion of the silver nitrate on metal-organic framework materials is realized, the C=C double bond in silver nitrate and ethylene forms π complexing
Key, the bond energy of π complex bonds are better than Van der Waals force, meanwhile, adsorbent material is higher than ethane for the adsorption capacity of ethylene, to realize
Separation to ethylene/ethane.
Compared with the prior art, technical solution of the present invention has the beneficial effect that
Preparation method of the present invention can effectively improve degree of scatter of the silver nitrate on metal organic framework carrier, to obtain
There must be the adsorbent material of more accessible active metal sites, and then improve adsorbent material and the separation of ethylene/ethane is selected
Select performance；In addition, preparation method is simple by the present invention, it is easy to accomplish, it has a good application prospect.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of adsorbent material made from three kinds of methods.
Specific embodiment
Technical solution of the present invention is described further combined with specific embodiments below.
Adsorbent material of the present invention on nitric acid modified by silver to carrier, will obtain load nitric acid using metal organic framework as carrier
The metal organic framework adsorbent material of silver.The process that the present invention modifies silver nitrate on carrier is Double solvent method, by by carrier
It is scattered in hydrophobic n-hexane solvent, so that hydrophilic silver nitrate solution enters inside the duct of carrier, realizes nitric acid
High degree of dispersion of the silver on carrier,
Embodiment 1
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 0.2857g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance to ethylene is 58.3cm3g-1, the adsorbance to ethane is 36.2cm3g-1。
Embodiment 2
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 0.4285g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance to ethylene is 60.5cm3g-1, the adsorbance to ethane is 34.3cm3g-1。
Embodiment 3
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 0.5714g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 62.4cm3g-1, the adsorbance to ethane is 32.5cm3g-1。
Embodiment 4
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 0.7142g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 63.6cm3g-1, the adsorbance to ethane is 26.5cm3g-1。
Embodiment 5
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 0.8571g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 64.5cm3g-1, the adsorbance to ethane is 23.9cm3g-1。
Embodiment 6
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.0g silver nitrate is dissolved in 1mL water), mixed solution is stirred
It is filtered after 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is in high-purity argon gas
The lower 105 DEG C of heat treatment 12h of atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 66.1cm3g-1, the adsorbance to ethane is 19.0cm3g-1。
Embodiment 7
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.1428g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 75.5cm3g-1, the adsorbance to ethane is 17.3cm3g-1。
Embodiment 8
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.2857g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 68.4cm3g-1, the adsorbance to ethane is 16.8cm3g-1。
Embodiment 9
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.4285g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 64.7cm3g-1, the adsorbance to ethane is 16.6cm3g-1。
Embodiment 10
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.1428g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of helium atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 74.3cm3g-1, the adsorbance to ethane is 18.2cm3g-1。
Embodiment 11
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.1428g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 12h of nitrogen atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 72.6cm3g-1, the adsorbance to ethane is 19.5cm3g-1。
Embodiment 12
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.1428g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 6h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 71.8cm3g-1, the adsorbance to ethane is 19.8cm3g-1。
Embodiment 13
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.1428g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 4h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 71.2cm3g-1, the adsorbance to ethane is 20.4cm3g-1。
Embodiment 14
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, is added with microsyringe into the hexane solution for be dispersed with metal organic framework
140uL silver nitrate solution (silver nitrate solution is made and 1.1428g silver nitrate is dissolved in 1mL water), by mixed solution
It is filtered after stirring 2h, then the sample obtained after filtering is dried into 2h at 40 DEG C of vacuum oven, the sample after drying is high-purity
The lower 105 DEG C of heat treatment 1h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 69.3cm3g-1, the adsorbance to ethane is 21.5cm3g-1。
Embodiment 15
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, 60uL is added into the hexane solution for be dispersed with metal organic framework with microsyringe
Silver nitrate solution (silver nitrate solution is made and 1.1428g silver nitrate is dissolved in 1mL water), stirs 2h for mixed solution
After filter, then by the sample obtained after filtering at 40 DEG C of vacuum oven dry 2h, it is dry after sample in high-purity argon atmosphere
Enclose lower 105 DEG C of heat treatment 12h.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 38.4cm3g-1, the adsorbance to ethane is 23.3cm3g-1。
Embodiment 16
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 of 12h, is added in 20mL n-hexane, is stirred for 2h after ultrasonic 15min, obtains being dispersed with gold
The hexane solution for belonging to organic backbone, 50uL is added into the hexane solution for be dispersed with metal organic framework with microsyringe
Silver nitrate solution (silver nitrate solution is made and 1.1428g silver nitrate is dissolved in 1mL water), stirs 2h for mixed solution
After filter, then by the sample obtained after filtering at 40 DEG C of vacuum oven dry 2h, it is dry after sample in high-purity argon atmosphere
Enclose lower 105 DEG C of heat treatment 12h.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 34.7cm3g-1, the adsorbance to ethane is 25.6cm3g-1。
Comparative example 1
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing 0.1g and activated in 150 DEG C of vacuum oven
The metal organic framework MIL-101 and silver nitrate 0.16g of 12h, grinds 30min at room temperature after being sufficiently mixed, will after grinding
Mixed material 105 DEG C of heat treatment 12h under high-purity argon gas atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 19.4cm3g-1, the adsorbance to ethane is 13.9cm3g-1。
Comparative example 2
It prepares the metal organic framework adsorbent material of nitric acid modified by silver: weighing silver nitrate 0.16g in beaker, 10mL is added
Water stirring, dissolves silver nitrate sufficiently, obtains silver nitrate solution；It weighs 0.1g and activates 12h's in 150 DEG C of vacuum oven
MIL-101 is added in silver nitrate solution, the heating water bath at 50 DEG C, after water evaporation is complete, takes out sample, sample is high-purity
The lower 105 DEG C of heat treatment 12h of argon atmosphere.
Adsorption capacity of the test material to ethylene/ethane: using Belsorp max test adsorbent material to ethylene/ethane
Adsorption capacity；The test condition of the adsorbent material is 25 DEG C, and pressure limit is 0~100kPa.Adsorbent material is in 100kPa
Adsorbance for ethylene is 56.1cm3g-1, the adsorbance to ethane is 17.9cm3g-1。
By Examples 1 to 9 it is found that silver nitrate introduction volume is different, performance is selected to the adsorbing separation of final adsorbent material
Influence is very big, and when silver nitrate introduction volume is 1.1428g, adsorbent material is best to the adsorbing separation selection performance of ethylene/ethane；It is logical
Embodiment 7,10,11 is crossed it is found that the selection of inert atmosphere has little effect the performance of adsorbent material；By embodiment 7,
12,13,14 it is found that influence of the heat treatment time to adsorbent material performance is not very big；By embodiment 7,15,16 it is found that working as
When silver nitrate introduction volume is 1.1428g, silver nitrate solution is added into the hexane solution for be dispersed with metal organic framework
Volume influences adsorbent material adsorbing separation selection performance very big.
The metal organic framework adsorbent material of middle loaded Ag (I) compared with the prior art, on the one hand its absorption to ethylene
Measure it is low, all in 20cm3g-1Left and right, it is on the other hand, low to the separation selectivity of ethylene/ethane, generally 14.2~21.3, no
Pipe is from adsorbance or separation selectivity all well below metal organic framework adsorbent material made from the method for the present invention.
As shown in Figure 1, embodiment 7 is AgNO do not occur on map using adsorbent material made from Double solvent method3's
Characteristic peak；And adsorbent material made from grinding or infusion process is used, there is very strong AgNO on map3Diffraction maximum.Thus illustrate,
AgNO in Double solvent method3Realize high degree of dispersion.
Claims (7)
1. a kind of preparation method of the metal organic framework adsorbent material of nitric acid modified by silver, it is characterised in that: this method specifically:
Silver nitrate solution is added dropwise in the n-hexane for being dispersed with metal organic framework, is placed in mixed material after being sufficiently mixed lazy
Property atmosphere in not higher than being heat-treated at a temperature of 105 DEG C, obtain the metal organic framework adsorbent material of nitric acid modified by silver.
2. the preparation method of the metal organic framework adsorbent material of nitric acid modified by silver according to claim 1, feature exist
In: the temperature of heat treatment is 100 DEG C~105 DEG C, and heat treatment time is 1~12 hour.
3. the preparation method of the metal organic framework adsorbent material of nitric acid modified by silver according to claim 1, feature exist
In: atmosphere of inert gases is one of high-purity argon gas, high pure nitrogen or high-purity helium.
4. the preparation method of the metal organic framework adsorbent material of nitric acid modified by silver according to claim 1, feature exist
In: one of model MIL-101, ZIF-8 of the metal organic framework or HKUST-1.
5. the preparation method of the metal organic framework adsorbent material of nitric acid modified by silver according to claim 1, feature exist
In: in mixed material, the mixing mass ratio of silver nitrate and metal-organic framework materials is 0.4~2: 1.
6. adsorbent material made from the preparation method of the metal organic framework adsorbent material of nitric acid modified by silver described in claim 1 exists
Application in terms of adsorbing separation ethylene/ethane.
7. adsorption material made from the preparation method of the metal organic framework adsorbent material of nitric acid modified by silver according to claim 6
Expect the application in terms of adsorbing separation ethylene/ethane, it is characterised in that: the use condition of the adsorbent material are as follows: at 25 DEG C,
Pressure limit is that 0~100kPa adsorbs ethylene/ethane mixed gas.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181881A (en) * | 2021-04-29 | 2021-07-30 | 郑州大学 | Novel ZIF-8@ Ag complex core-shell structure hybrid material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120004491A1 (en) * | 2010-06-30 | 2012-01-05 | Uop Llc | Adsorptive Process for Separation of C8 Aromatic Hydrocarbons |
| CN103058810A (en) * | 2013-01-15 | 2013-04-24 | 中国石油大学(北京) | Method for separating ethane and ethylene in mixed gas |
| CN103193578A (en) * | 2013-04-08 | 2013-07-10 | 浙江师范大学 | Method for separating propylene and propane by utilizing metal-organic framework material |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| CN104492383A (en) * | 2014-12-09 | 2015-04-08 | 浙江大学 | Metal organic framework adsorbent as well as preparation method and application thereof |
| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
| US9108891B1 (en) * | 2014-11-21 | 2015-08-18 | Chevron Phillips Chemical Company | Ethylene separation with pressure swing adsorption |
| CN106807446A (en) * | 2017-02-06 | 2017-06-09 | 辽宁大学 | A kind of composites of Ag@MIL 101 and its preparation method and application |
| CN109395697A (en) * | 2018-11-16 | 2019-03-01 | 武汉理工大学 | A kind of preparation method carrying silver-colored adsorbent and its application in water body containing iodine |
-
2019
- 2019-06-13 CN CN201910512978.9A patent/CN110237816B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120004491A1 (en) * | 2010-06-30 | 2012-01-05 | Uop Llc | Adsorptive Process for Separation of C8 Aromatic Hydrocarbons |
| CN103058810A (en) * | 2013-01-15 | 2013-04-24 | 中国石油大学(北京) | Method for separating ethane and ethylene in mixed gas |
| CN103193578A (en) * | 2013-04-08 | 2013-07-10 | 浙江师范大学 | Method for separating propylene and propane by utilizing metal-organic framework material |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| US9108891B1 (en) * | 2014-11-21 | 2015-08-18 | Chevron Phillips Chemical Company | Ethylene separation with pressure swing adsorption |
| CN104492383A (en) * | 2014-12-09 | 2015-04-08 | 浙江大学 | Metal organic framework adsorbent as well as preparation method and application thereof |
| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
| CN106807446A (en) * | 2017-02-06 | 2017-06-09 | 辽宁大学 | A kind of composites of Ag@MIL 101 and its preparation method and application |
| CN109395697A (en) * | 2018-11-16 | 2019-03-01 | 武汉理工大学 | A kind of preparation method carrying silver-colored adsorbent and its application in water body containing iodine |
Non-Patent Citations (3)
| Title |
|---|
| LEI YU ET AL: "Experimental Study of Silver-Loaded Mesoporous Silica for the Separation of Ethylene and Ethane", 《J. CHEM. ENG. DATA》 * |
| YU YIN ET AL: "Confinement of Ag(I) Sites within MIL-101 for Robust Ethylene/Ethane Separation", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| ZHANG, YIMING ET AL: "Highly selective adsorption of ethylene over ethane in a MOF featuring the combination of open metal site and pi-complexation", 《CHEMICAL COMMUNICATIONS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181881A (en) * | 2021-04-29 | 2021-07-30 | 郑州大学 | Novel ZIF-8@ Ag complex core-shell structure hybrid material and preparation method and application thereof |
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