CN114367270A - Method for separating acetylene and carbon dioxide - Google Patents

Method for separating acetylene and carbon dioxide Download PDF

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CN114367270A
CN114367270A CN202111440996.4A CN202111440996A CN114367270A CN 114367270 A CN114367270 A CN 114367270A CN 202111440996 A CN202111440996 A CN 202111440996A CN 114367270 A CN114367270 A CN 114367270A
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carbon dioxide
acetylene
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organic framework
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鲍宗必
郑芳
任其龙
张治国
杨亦文
杨启炜
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Zhejiang University ZJU
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Abstract

The application relates to a method for separating acetylene and carbon dioxide, which comprises the step of carrying out adsorption separation on a mixed gas containing acetylene and carbon dioxide by taking a metal organic framework material as an adsorbent, wherein the metal organic framework material comprises a two-dimensional layered structure formed by metal ions, a compound shown as a formula I and pillared anions, and in the formula I, R is1To R8Each independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, or halogen. The metal organic framework material adopted in the method has the advantages of good stability, high adsorption and separation selectivity, simple preparation method and low preparation cost.
Figure DDA0003383360700000011

Description

Method for separating acetylene and carbon dioxide
Technical Field
The present application relates to a method of separating acetylene and carbon dioxide.
Background
Acetylene (C)2H2) As the simplest acetylenes, widely used for the production of several commercial fine chemicals, such as methyl acrylate, butynediol, ethylene derivatives, acetylene alcohols and electronics, are one of the most critical raw materials in the petrochemical industry. In addition, acetylene is also used as a gaseous fuel for oxyacetylene flames for welding and metal cutting. In the petrochemical industry, the coupling of methane in the presence of oxygen produces acetylene, and during the oxidative coupling reaction to produce acetylene, the acetylene product often contains carbon dioxide (CO)2) Impurities. Therefore, it must be selected from C2H2Carbon dioxide is removed from the product, which is one of the most important industrial separations. At the same time, due to C2H2And CO2The molecules are in linear shape and the molecular size is respectively
Figure BDA0003383360680000011
And
Figure BDA0003383360680000012
they have the same kinetic diameter
Figure BDA0003383360680000013
And close boiling point (C)2H2And CO2189.3K and 194.7K, respectively) cause separation to be difficult. Conventional C2H2/CO2The separation technique is based on solvent extraction of acetone and n-methylpyrrolidone. From the viewpoint of energy saving and environmental protection, the adsorption separation technology will be the future C2H2/CO2An important technique for separation, among which gas storage and separation using porous materials has become the most important techniqueOne of the useful techniques.
Traditional porous materials, such as zeolite molecular sieves, clays, activated carbon, etc., are generally less selective at ambient temperature and pressure, and the separation performance of adsorbents with lower adsorption capacity depends on the pore structure and pore surface properties of the adsorbent and the physicochemical properties of the adsorbed gas. A Metal-organic framework (MOF) (also called porous coordination polymer) is a porous crystal material consisting of Metal nodes and bridging organic ligands, has the advantages of extremely high specific surface area and pore volume, low density, high designability and the like, and has very wide application prospect in the field of gas separation.
At present, the application of metal organic framework materials in acetylene carbon dioxide separation is receiving attention of more and more researchers, and how to prepare a novel metal organic framework material which can be used for acetylene carbon dioxide separation and has good stability, high adsorption capacity and adsorption separation selectivity at low cost is a very challenging technical problem.
Disclosure of Invention
Aiming at the defects of the prior art, the inventor of the application finds that acetylene and carbon dioxide can be efficiently adsorbed and separated by adopting a special metal organic framework material through a large amount of researches, and the metal organic framework material has the advantages of good stability, high adsorption and separation selectivity, simple preparation method and low preparation cost.
Therefore, the application provides a method for separating acetylene and carbon dioxide, which comprises the step of carrying out adsorption separation on a mixed gas containing acetylene and carbon dioxide by taking a metal organic framework material as an adsorbent, wherein the metal organic framework material comprises a two-dimensional layered structure formed by metal ions, a compound shown in a formula I and pillared anions,
Figure BDA0003383360680000021
in the formula I, R1To R8Each independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, or halogen.
According to some embodiments of the application, R in formula I1To R8Each independently selected from hydrogen or C1-C3 alkyl. In some embodiments, the compound of formula I is 4,4' -dipyridyldithio.
According to some embodiments of the present application, the metal ion is selected from Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Mg2+、Ca2+Or Mn2+One or more of (a).
According to some embodiments of the present application, the pillared anion is selected from CrO4 2-、MoO4 2-、WO4 2-、Cr2O7 2-One or more of (a).
According to some embodiments of the present application, the metal-organic framework material may be in the shape of a block, a column, a particle, or a film.
According to some embodiments of the present application, the method of preparing the metal-organic framework material comprises: reacting a metal inorganic salt, a compound of formula I, and an inorganic oxoacid salt in a solvent to produce the metal-organic framework material. In the application, the metal inorganic salt, the compound shown in the formula I and the inorganic oxysalt form a two-dimensional layered structure through coordination bonds and intermolecular interaction forces. In the preparation process of the metal organic framework material, a cheap and easily-obtained compound shown in the formula I, such as 4,4' -dipyridyl disulfide, is used as an organic ligand to react with a series of metal inorganic salts in water and an organic solvent, such as acetonitrile, the price of a preparation raw material is low, the synthesis condition is mild, the operation is simple, the post-treatment is easy, the material synthesis cost is low, the prepared metal organic framework material has high adsorption and separation selectivity on acetylene and carbon dioxide, the material structure and the adsorption performance are stable, the stability in a water vapor-containing environment is good, and the industrial application prospect is good.
According to some embodiments of the present application, the metal inorganic salt is selected from one or more of chloride, nitrate, acetate, carbonate, sulfate or perchlorate. According to a preferred embodiment of the present application, the metal inorganic salt is selected from one or more of nickel chloride, manganese chloride or cobalt chloride.
According to some embodiments of the present application, the inorganic oxyacid salt is selected from one or more of chromate, molybdate, tungstate, or dichromate. According to a preferred embodiment of the present application, the inorganic oxo acid salt is selected from one or more of sodium chromate, potassium chromate, magnesium chromate, calcium chromate, lead chromate, silver chromate, ammonium chromate, sodium molybdate, potassium molybdate, ammonium molybdate, nickel molybdate, cobalt molybdate, manganese molybdate, sodium tungstate, potassium tungstate, calcium tungstate, cobalt tungstate, cadmium tungstate, ferrous tungstate, ammonium tungstate or zinc tungstate. According to a further preferred embodiment of the present application, the inorganic oxyacid salt is selected from one or more of sodium chromate, potassium chromate, ammonium chromate, sodium molybdate, potassium molybdate, ammonium molybdate, sodium tungstate, potassium tungstate or ammonium tungstate. The inorganic oxysalt adopted in the application has the advantages of cheap and easily obtained raw materials.
According to some embodiments of the present application, the molar ratio of the compound of formula I to the inorganic oxoacid salt, based on the metal ion, of the metal inorganic salt is 1 (1-5) to (1-5). According to the preferred embodiment of the application, the molar ratio of the compound shown in the formula I to the inorganic oxysalt is 1 (1-3) to (1-3) in terms of metal ions of the metal inorganic salt. Further preferably, the molar ratio of the compound represented by the formula I to the inorganic oxysalt is 1:2:1, calculated as metal ions, of the metal inorganic salt. In the application, the change of the ratio of the metal inorganic salt, the compound shown in the formula I and the inorganic oxysalt can change the size, crystal form, regularity and the like of crystals, and can also influence the adsorption capacity and selective separation performance of the metal organic framework material on acetylene carbon dioxide gas.
According to some embodiments of the present application, the solvent comprises an organic solvent selected from one or more of methanol, ethanol, acetonitrile, acetone, N-dimethylformamide or N, N-dimethylacetamide, and water. According to a preferred embodiment of the present application, the organic solvent is selected from one or more of methanol, ethanol or acetonitrile. According to a further preferred embodiment of the present application, the organic solvent is acetonitrile. The organic solvents adopted in the application have the advantages of low toxicity, low price and easy obtainment.
According to some embodiments of the present application, the volume ratio of the organic solvent to water is 1 (0.1-5), and may be, for example, 1:0.1, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, and any value therebetween.
According to some embodiments of the present application, the reaction is at a temperature of 10 ℃ to 120 ℃ for a time of 0.5 hours to 48 hours. According to a preferred embodiment of the present application, the temperature of the reaction is from 10 ℃ to 50 ℃ and the time is from 0.5 hours to 24 hours. According to a further preferred embodiment of the present application, the reaction is carried out at room temperature for a period of 12 hours.
According to some embodiments of the present application, the preparation method further comprises purifying and vacuum drying the metal-organic framework material as a solid product after the reaction is finished. According to some embodiments of the present application, the purifying step comprises: washing and filtering for several times by water to displace residual alkali solution and residual inorganic salt in the pore channel of the material, and washing and filtering for several times by organic solvent, preferably acetonitrile, to displace residual organic ligand and water in the pore channel. According to some embodiments of the present application, the vacuum drying is at a temperature of 30 ℃ to 120 ℃ for a time of 6 hours to 24 hours.
The method for adsorbing and separating acetylene and carbon dioxide has simple process, and can be used for adsorbing and separating the mixed gas under certain pressure by an adsorption tower or an adsorption column filled with the adsorbent containing the metal organic framework material, and further the adsorption tower can also be composed of one or more than one adsorbent, and the separation is realized by adopting the existing pressure swing adsorption or vacuum pressure swing adsorption or temperature swing adsorption. The metal organic framework material has an in-layer pore channel and an interlayer pore channel, strong adsorption sites are provided for uncoordinated anions in the pore channel, acetylene with negative charges at two ends can enter or open the pore channel to have strong interaction with functional groups on the surface of the material, carbon dioxide with positive charges at two ends is not beneficial to entering the pore channel, the pore channel is opened without enough energy for small holes, and relatively weak adsorption exists for larger holes, so that the acetylene and the carbon dioxide are separated.
According to some embodiments of the present application, the temperature of the adsorptive separation is from-5 ℃ to 50 ℃, preferably from 20 ℃ to 50 ℃.
According to some embodiments of the present application, the total pressure of the mixed gas is 10kPa to 3000kPa, preferably 100kPa to 1000kPa, and more preferably 100kPa to 400kPa
In some embodiments of the present application, when the pillared anion of the metal-organic framework material is chromate ion, the temperature of adsorptive separation is 25 ℃, and the total pressure of the mixed gas is 100 kPa; when the pillared anions of the metal-organic framework material are molybdate ions and tungstate ions, the temperature for adsorption and separation is 0 ℃, and the total pressure of the mixed gas is 100 kPa.
In some embodiments of the present application, the adsorptive separation comprises the steps of: filling a metal organic framework material into the packed column; passing a mixed gas containing acetylene and carbon dioxide through a packed column; the interaction force of the carbon dioxide and the metal organic framework material is weaker and flows out from the tail end of the packed column more quickly, and the interaction force of the acetylene and the metal organic framework material is stronger and flows out from the tail end of the packed column slowly after the adsorption is saturated. Due to the fact that the interaction force of the metal organic framework material to the two gases is different, effective separation of acetylene and carbon dioxide mixed gas is achieved. Preferably, the flow rate of the mixed gas passing through the packed column is 1mL/min to 10 mL/min.
In the present application, the gas mixture to be separated is not limited to acetylene and carbon dioxide, but may also contain other gases such as methane, nitrogen, ethane, helium, etc. The raw material gas has wide composition range, and various concentrations can be applicable, and can be from 50ppm to 65%. The preferred operating conditions for the adsorptive separation are a temperature of-5 ℃ to 50 ℃ and a total pressure of the mixed gas of 10kPa to 3000kPa, within which the selectivity of the adsorption is desired to exceed that of most existing adsorbents.
After the adsorbent is adsorbed and saturated, the regeneration can be realized only by heating to 50-120 ℃ at normal temperature or under the inert atmosphere conditions of vacuum or helium, nitrogen and the like and keeping for 10-72 hours. The adsorbent structure is damaged due to the fact that the heating temperature is too high or the heating time is too long; if the temperature is too low or the time is too short, the residual adsorbate in the adsorbent cannot be completely removed.
Compared with the prior art, the method has the following advantages:
in the method for separating acetylene and carbon dioxide, the adopted metal organic frame material has stable structure and stable performance, has very high adsorption selectivity on acetylene and carbon dioxide, and still keeps the original effect after repeated adsorption-regeneration. The raw materials for preparing the metal organic framework material are cheap and easy to obtain, the synthesis condition is mild, the purification step is simple, and the operation and amplification are easy. The adsorbent prepared by the method is far superior to most solid adsorbents in the aspect of adsorption separation of acetylene and carbon dioxide. In addition, the metal organic framework material has good stability in an environment containing water vapor, and still has a good adsorption separation effect after being soaked in a pure water environment for one week.
Drawings
FIG. 1 is the adsorption isotherm diagram of a single component of acetylene and carbon dioxide at 25 ℃ in example 1.
FIG. 2 is a graph showing the permeation profile of the mixed gas of acetylene and carbon dioxide in example 1.
FIG. 3 is the adsorption isotherm diagram of a single component of acetylene and carbon dioxide at 25 ℃ in example 2.
FIG. 4 is a graph showing the permeation profile of the mixed gas of acetylene and carbon dioxide in example 2.
FIG. 5 is the adsorption isotherm diagram of a single component of acetylene and carbon dioxide at 25 ℃ in example 3.
FIG. 6 is a graph showing the permeation profile of the mixed gas of acetylene and carbon dioxide in example 3.
FIG. 7 is the adsorption isotherm diagram of a single component of acetylene and carbon dioxide at 25 ℃ in example 4.
FIG. 8 is a graph showing the permeation profile of the mixed gas of acetylene and carbon dioxide in example 4.
FIG. 9 is the adsorption isotherm diagram of a single component of acetylene and carbon dioxide at 25 ℃ in example 5.
FIG. 10 is a graph showing the permeation profile of the mixed gas of acetylene and carbon dioxide in example 5.
FIG. 11 is the adsorption isotherm diagram of a single component of acetylene and carbon dioxide at 25 ℃ in example 6.
FIG. 12 is a graph showing the permeation profile of the mixed gas of acetylene and carbon dioxide in example 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, the reagents and instruments used were not designated by the manufacturer, and were all conventional products commercially available.
Example 1
Dropwise adding a mixed solution of deionized water containing 2mmol of 4,4' -dithiodipyridine and acetonitrile (v: v ═ 1:2) into an isovolumetric aqueous solution containing 1mmol of nickel chloride hexahydrate and 1mmol of potassium chromate, carrying out reaction at room temperature, and washing the obtained solid in sequence with deionized water and acetonitrile for multiple times to obtain the purified metal organic framework material. The purified metal organic framework material is used as an adsorbent, vacuum degassing is carried out for 12 hours at 80 ℃ to obtain a desolventized adsorbent, and then gas adsorption is carried out.
In order to test the adsorption separation performance of the synthesized metal organic framework material, a single component adsorption isotherm of acetylene carbon dioxide was performed using the adsorbent. 100mg of adsorbent was taken, and the adsorption temperature was set at 25 ℃. The single component adsorption isotherm is shown in figure 1. According to the test, the adsorption amount of acetylene reaches 2.98mmol/g and the adsorption amount of carbon dioxide reaches 1.57mmol/g at 25 ℃ and 100kPa, the adsorption amount of acetylene reaches 2.78mmol/g and the adsorption amount of carbon dioxide reaches 0.98mmol/g at 10kPa, and the adsorption selectivity of the adsorbent to two gases at 100kPa reaches 67.7 at an acetylene/carbon dioxide ratio of 50:50 calculated by IAST.
In order to test the stability of the synthesized metal organic framework material, the metal organic framework material was exposed to air with a relative humidity of 60% for 7 days and then subjected to crystal structure analysis after 7 days in water, and the obtained solid structure was found to maintain a good crystal form.
In order to test the practical effect of the metal organic framework material on the separation of acetylene and carbon dioxide, a penetration experiment of a mixed gas of acetylene and carbon dioxide was performed by using the synthesized adsorbent. In the embodiment, the mixed gas of acetylene and carbon dioxide is absorbed and separated, the volume ratio is 50:50, the penetrating temperature is 25 ℃, and the pressure is 0.1 MPa. The penetration curve is shown in figure 2. It was tested that at a volume ratio of acetylene to carbon dioxide of 50:50, carbon dioxide penetrated in 33 minutes and acetylene started penetrating in 79 minutes. The two mixed gases are effectively separated. The metal organic framework material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
Example 2
Dropwise adding a mixed solution of deionized water containing 2mmol of 4,4' -dithiodipyridine and acetonitrile (v: v ═ 1:2) into an isovolumetric aqueous solution containing 1mmol of nickel chloride hexahydrate and 1mmol of sodium molybdate, reacting at room temperature, and washing the solid obtained by the reaction with deionized water and acetonitrile for multiple times to obtain the purified metal organic framework material. The purified metal organic framework material is used as an adsorbent, vacuum degassing is carried out for 12 hours at 80 ℃ to obtain a desolventized adsorbent, and then gas adsorption is carried out.
In order to test the adsorption separation performance of the synthesized metal organic framework material, a single component adsorption isotherm of acetylene carbon dioxide was performed using the adsorbent. 100mg of the adsorbent is taken, and the adsorption temperature is set to be 25 ℃. The single component adsorption isotherm is shown in figure 3. According to the test, the adsorption amount of acetylene reaches 2.76mmol/g and the adsorption amount of carbon dioxide reaches 1.98mmol/g at 25 ℃ and 100kPa, the adsorption amount of acetylene reaches 1.79mmol/g and the adsorption amount of carbon dioxide reaches 1.37mmol/g at 10kPa, and the adsorption selectivity of the adsorbent to two gases at 100kPa reaches 14.5 at an acetylene/carbon dioxide ratio of 50:50 calculated by IAST.
In order to test the stability of the synthesized metal organic framework material, the metal organic framework material was exposed to air with a relative humidity of 60% for 7 days and then subjected to crystal structure analysis after 7 days in water, and the obtained solid structure was found to maintain a good crystal form.
In order to test the practical effect of the metal organic framework material on the separation of acetylene and carbon dioxide, a penetration experiment of a mixed gas of acetylene and carbon dioxide was performed by using the synthesized adsorbent. In the embodiment, the mixed gas of acetylene and carbon dioxide is absorbed and separated, the volume ratio is 50:50, the penetrating temperature is 25 ℃, and the pressure is 0.1 MPa. The penetration curve is shown in figure 4. It was tested that at a volume ratio of acetylene to carbon dioxide of 50:50, carbon dioxide breakthrough occurred in 39 minutes and acetylene began to breakthrough in 62 minutes. The two mixed gases are effectively separated. The metal organic framework material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
Example 3
Dropwise adding a mixed solution of deionized water containing 2mmol of 4,4' -dithiodipyridine and acetonitrile (v: v ═ 1:2) into an isovolumetric aqueous solution containing 1mmol of nickel chloride hexahydrate and 1mmol of sodium tungstate, reacting at room temperature, and washing the obtained solid by deionized water and acetonitrile sequentially for multiple times to obtain the purified metal-organic framework material. The purified metal organic framework material is used as an adsorbent, vacuum degassing is carried out for 12 hours at 80 ℃ to obtain a desolventized adsorbent, and then gas adsorption is carried out.
In order to test the adsorption separation performance of the synthesized metal organic framework material, a single component adsorption isotherm of acetylene carbon dioxide was performed using the adsorbent. 100mg of the adsorbent is taken, and the adsorption temperature is set to be 25 ℃. The single component adsorption isotherm is shown in fig. 5. Tests show that the adsorption quantity of acetylene reaches 2.05mmol/g and the adsorption quantity of carbon dioxide reaches 1.43cm at 25 ℃ and 100kPa3The adsorption selectivity of the adsorbent to two gases at 100kPa is 20.9 when the ratio of acetylene to carbon dioxide is 50:50 calculated by IAST, and the adsorption amount of acetylene is 1.28mmol/g and the adsorption amount of carbon dioxide is 0.97mmol/g at low pressure of 10 kPa.
In order to test the stability of the synthesized metal organic framework material, the metal organic framework material was exposed to air with a relative humidity of 60% for 7 days and then subjected to crystal structure analysis after 7 days in water, and the obtained solid structure was found to maintain a good crystal form.
In order to test the practical effect of the metal organic framework material on the separation of acetylene and carbon dioxide, a penetration experiment of a mixed gas of acetylene and carbon dioxide was performed by using the synthesized adsorbent. In the embodiment, the mixed gas of acetylene and carbon dioxide is absorbed and separated, the volume ratio is 50:50, the penetrating temperature is 25 ℃, and the pressure is 0.1 MPa. The penetration curve is shown in figure 6. It was tested that at a volume ratio of acetylene to carbon dioxide of 50:50, carbon dioxide breakthrough occurred in 18 minutes and acetylene began breakthrough in 32 minutes. The two mixed gases are effectively separated. The metal organic framework material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
Example 4
Dropwise adding a mixed solution of deionized water containing 2mmol of 4,4' -dithiodipyridine and acetonitrile (v: v ═ 1:2) into an isovolumetric aqueous solution containing 1mmol of cobalt chloride hexahydrate and 1mmol of potassium chromate, carrying out reaction at room temperature, and washing the obtained solid in sequence with deionized water and acetonitrile for multiple times to obtain the purified metal organic framework material. The purified metal organic framework material is used as an adsorbent, vacuum degassing is carried out for 12 hours at 80 ℃ to obtain a desolventized adsorbent, and then gas adsorption is carried out.
In order to test the adsorption separation performance of the synthesized metal organic framework material, a single component adsorption isotherm of acetylene carbon dioxide was performed using the adsorbent. 100mg of the adsorbent is taken, and the adsorption temperature is set to be 25 ℃. The single component adsorption isotherm is shown in figure 7. It was found that the adsorption amount of acetylene and the adsorption amount of carbon dioxide reached 2.43mmol/g and 0.47mmol/g at 25 ℃ and 100kPa, and that the adsorption amount of acetylene and the adsorption amount of carbon dioxide reached 0.81mmol/g and 0.23mmol/g at a low pressure of 10 kPa.
In order to test the stability of the synthesized metal organic framework material, the metal organic framework material was exposed to air with a relative humidity of 60% for 7 days and then subjected to crystal structure analysis after 7 days in water, and the obtained solid structure was found to maintain a good crystal form.
In order to test the practical effect of the metal organic framework material on the separation of acetylene and carbon dioxide, a penetration experiment of a mixed gas of acetylene and carbon dioxide was performed by using the synthesized adsorbent. In the embodiment, the mixed gas of acetylene and carbon dioxide is absorbed and separated, the volume ratio is 50:50, the penetrating temperature is 25 ℃, and the pressure is 0.1 MPa. The penetration curve is shown in figure 8. It was tested that at a volume ratio of acetylene to carbon dioxide of 50:50, carbon dioxide breakthrough occurred in 17 minutes and acetylene began breakthrough in 47 minutes. The two mixed gases are effectively separated. The metal organic framework material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
Example 5
Dropwise adding a mixed solution of deionized water containing 2mmol of 4,4' -dithiodipyridine and acetonitrile (v: v ═ 1:2) into an isovolumetric aqueous solution containing 1mmol of cobalt chloride hexahydrate and 1mmol of sodium molybdate, reacting at room temperature, and washing the solid obtained by the reaction with deionized water and acetonitrile for multiple times in sequence to obtain the purified metal organic framework material. The purified metal organic framework material is used as an adsorbent, vacuum degassing is carried out for 12 hours at 80 ℃ to obtain a desolventized adsorbent, and then gas adsorption is carried out.
In order to test the adsorption separation performance of the synthesized metal organic framework material, a single component adsorption isotherm of acetylene carbon dioxide was performed using the adsorbent. 100mg of the adsorbent is taken, and the adsorption temperature is set to be 25 ℃. The single component adsorption isotherm is shown in fig. 9. According to the test, the adsorption amount of acetylene reaches 2.72mmol/g, the adsorption amount of carbon dioxide reaches 0.32mmol/g, and the opening pressure is about 20kPa at 25 ℃ and 100 kPa.
In order to test the stability of the synthesized metal organic framework material, the metal organic framework material was exposed to air with a relative humidity of 60% for 7 days and then subjected to crystal structure analysis after 7 days in water, and the obtained solid structure was found to maintain a good crystal form.
In order to test the practical effect of the metal organic framework material on the separation of acetylene and carbon dioxide, a penetration experiment of a mixed gas of acetylene and carbon dioxide was performed by using the synthesized adsorbent. In the embodiment, the mixed gas of acetylene and carbon dioxide is absorbed and separated, the volume ratio is 50:50, the penetrating temperature is 25 ℃, and the pressure is 0.1 MPa. The penetration curve is shown in figure 10. Tests show that when the volume ratio of acetylene to carbon dioxide is 50:50, acetylene leaks due to the flexibility of the opening. The two mixed gases are effectively separated as the penetration is carried out. The metal organic framework material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
Example 6
Dropwise adding a mixed solution of deionized water containing 2mmol of 4,4' -dithiodipyridine and acetonitrile (v: v ═ 1:2) into an isovolumetric aqueous solution containing 1mmol of cobalt chloride hexahydrate and 1mmol of sodium tungstate, reacting at room temperature, and washing the obtained solid by deionized water and acetonitrile sequentially for multiple times to obtain the purified metal organic framework material. The purified metal organic framework material is used as an adsorbent, vacuum degassing is carried out for 12 hours at 80 ℃ to obtain a desolventized adsorbent, and then gas adsorption is carried out.
In order to test the adsorption separation performance of the synthesized metal organic framework material, a single component adsorption isotherm of acetylene carbon dioxide was performed using the adsorbent. 100mg of the adsorbent is taken, and the adsorption temperature is set to be 25 ℃. The single component adsorption isotherm is shown in fig. 11. According to the test, the adsorption amount of acetylene reaches 2.2mmol/g, the adsorption amount of carbon dioxide reaches 0.40mmol/g, and the opening pressure is about 10kPa at 25 ℃ and 100 kPa.
In order to test the stability of the synthesized metal organic framework material, the metal organic framework material was exposed to air with a relative humidity of 60% for 7 days and then subjected to crystal structure analysis after 7 days in water, and the obtained solid structure was found to maintain a good crystal form.
In order to test the practical effect of the metal organic framework material on the separation of acetylene and carbon dioxide, a penetration experiment of a mixed gas of acetylene and carbon dioxide was performed by using the synthesized adsorbent. In the embodiment, the mixed gas of acetylene and carbon dioxide is absorbed and separated, the volume ratio is 50:50, the penetrating temperature is 25 ℃, and the pressure is 0.1 MPa. The penetration curve is shown in figure 12. Tests show that when the volume ratio of acetylene to carbon dioxide is 50:50, acetylene leaks due to the flexibility of the opening. The two mixed gases are effectively separated as the penetration is carried out. The metal organic framework material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
It should be noted that the above-mentioned embodiments are only for explaining the present application and do not constitute any limitation to the present application. The present application has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the present application as specified within the scope of the claims of the present application and modifications may be made to the present application without departing from the scope and spirit of the present application. Although the present application has been described herein with reference to particular means, materials and embodiments, the present application is not intended to be limited to the particulars disclosed herein, but rather the present application extends to all other methods and applications having the same functionality.

Claims (10)

1. A method for separating acetylene and carbon dioxide comprises the steps of taking a metal organic framework material as an adsorbent, and carrying out adsorption separation on a mixed gas containing acetylene and carbon dioxide, wherein the metal organic framework material comprises a two-dimensional layered structure formed by metal ions, a compound shown in a formula I and pillared anions,
Figure FDA0003383360670000011
in the formula I, R1To R8Each independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, or halogen.
2. The method of claim 1, wherein in formula I, R is1To R8Each independently selected from hydrogen or C1-C3 alkyl.
3. Method according to claim 1 or 2, characterized in that the metal isThe ions being selected from Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Mg2+、Ca2+Or Mn2+And/or the pillared anion is selected from CrO4 2-、MoO4 2-、WO4 2-、Cr2O7 2-One or more of (a).
4. The method according to any one of claims 1-3, wherein the method for preparing the metal-organic framework material comprises: reacting a metal inorganic salt, a compound of formula I, and an inorganic oxoacid salt in a solvent to produce the metal-organic framework material.
5. The method according to claim 4, wherein the metal inorganic salt is selected from one or more of chloride, nitrate, acetate, carbonate, sulfate or perchlorate, preferably from one or more of nickel chloride, manganese chloride or cobalt chloride; and/or
The inorganic oxysalt is selected from one or more of chromate, molybdate, tungstate or dichromate, preferably from one or more of sodium chromate, potassium chromate, magnesium chromate, calcium chromate, lead chromate, silver chromate, ammonium chromate, sodium molybdate, potassium molybdate, ammonium molybdate, nickel molybdate, cobalt molybdate, manganese molybdate, sodium tungstate, potassium tungstate, calcium tungstate, cobalt tungstate, cadmium tungstate, ferrous tungstate, ammonium tungstate or zinc tungstate.
6. The method according to claim 4 or 5, wherein the molar ratio of the compound represented by the formula I to the inorganic oxysalt is 1 (1-5) to (1-5), preferably 1 (1-3) to (1-3), based on the metal ion of the metal inorganic salt.
7. The process according to any one of claims 4 to 6, wherein the solvent comprises an organic solvent selected from one or more of methanol, ethanol, acetonitrile, acetone, N-dimethylformamide or N, N-dimethylacetamide, and water; preferably, the volume ratio of the organic solvent to the water is 1 (0.1-5).
8. The process according to any one of claims 4 to 7, characterized in that the temperature of the reaction is from 10 ℃ to 120 ℃, preferably from 10 ℃ to 50 ℃; the reaction time is 0.5 to 48 hours, preferably 0.5 to 24 hours.
9. The method of any one of claims 1-8, wherein the temperature of the adsorptive separation is from-5 ℃ to 50 ℃.
10. The method of any one of claims 1-9, wherein the total pressure of the mixed gas is from 10kPa to 3000 kPa.
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