CN110451466B - Xenon krypton gas separation method - Google Patents

Xenon krypton gas separation method Download PDF

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CN110451466B
CN110451466B CN201910635964.6A CN201910635964A CN110451466B CN 110451466 B CN110451466 B CN 110451466B CN 201910635964 A CN201910635964 A CN 201910635964A CN 110451466 B CN110451466 B CN 110451466B
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xenon
krypton
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CN110451466A (en
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邢华斌
王青菊
杨启炜
崔希利
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Zhejiang University ZJU
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Abstract

The invention discloses a method for separating xenon from krypton, which adopts a flexible anion hybrid ultramicropore material containing fluorine to selectively adsorb xenon in xenon/krypton mixed gas so as to realize the separation of xenon and krypton; the general structural formula of the fluoride-containing anion hybrid ultramicropore material with the flexible function is M- (C)12H8N2)‑AF6Or M- (C)10H8N2S2)‑AF6(ii) a Wherein, C12H8N2Is an organic ligand 1, 2-dipyridyl acetylene, C10H8N2S2Is an organic ligand 4, 4' -dipyridyl disulfide, M is a metal ion, AF6Is an inorganic fluorine-containing anion. Compared with the conventional adsorbent, the fluoride anion hybrid ultramicropore material with the flexible function has the advantages of adjustable pore structure, adjustable action force with adsorbate molecules and the like, and simultaneously has high adsorption capacity and high selectivity.

Description

Xenon krypton gas separation method
Technical Field
The invention relates to the technical field of gas separation, in particular to a method for separating xenon and krypton.
Background
The inert gases xenon and krypton are important industrial gases in national economy, and have wide application in the fields of electronics, medicine, electric light sources, gas lasers, plasma streams, semiconductors and the like due to the special physical properties of the inert gases xenon and krypton. Xenon and krypton are mainly derived from air and are very low, only 0.087ppmv and 1 ppmv. At present, with economic recovery, the rapid development of new industries will greatly increase the demand of xenon and krypton.
Currently, high-purity xenon and krypton are produced industrially mainly by means of cryogenic rectification. In a large air separation plant, a high-concentration mixture of xenon and krypton is separated as a by-product, and in order to obtain high-purity xenon and krypton, the mixture needs to be separated by cryogenic rectification. However, the relative volatility of xenon and krypton is small, and the physical properties are similar, so that the traditional separation mode has the defects of high energy consumption, high cost, complex process and the like, and the industrial application of xenon and krypton is greatly limited. Therefore, there is a need to develop an efficient and energy-saving separation technology to realize the separation of xenon/krypton.
In recent years, due to the advantages of low energy consumption, simple operation, low production cost and the like, the adsorption separation technology based on the porous material is gradually replacing the traditional cryogenic rectification technology. The key point of the technology is to develop an adsorbent material with high capacity and high selectivity, but the existing adsorbent material often has the phenomenon that the high adsorption capacity and the high selectivity cannot be combined, and the industrial application value of the adsorbent material is seriously influenced.
For example, the adsorption capacity of the conventional solid adsorbent NaA molecular sieve for xenon is 20% -30%, the selectivity is only 4-6 (100kPa, 298K), and the lower adsorption capacity and selectivity limit the application thereof (J.chem.Phys,1997,107(11): 4364-4372). As another example, a porous organic molecular cage CC3 is used for separation of xenon and krypton, the adsorption amounts of CC3 to xenon and krypton are 2.42 and 0.92mmol/g (100kPa, 298K), the ratio of the adsorption amounts is only 2.63, and the separation selectivity is low (Nature Materials,2014,13(10): 954-960). In addition, SBMOF-2 shows a strong adsorption force for xenon, so that the adsorption capacity of xenon is increased to 2.83mmol/g (100kPa, 298K), but the separation selectivity is limited because it still has a certain adsorption amount (0.9mmol/g) for krypton (Journal of the American Chemical Society,2015,137(22): 7007-.
Therefore, the development of adsorbent materials with both high capacity and high selectivity to achieve efficient separation of xenon krypton remains a major challenge.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a method for separating xenon from krypton, which takes a fluorine-containing anion hybrid ultramicropore material with a flexible function as an adsorbent, and contacts with xenon/krypton mixed gas to selectively identify and capture xenon so as to realize the separation of xenon and krypton.
A method for separating xenon from krypton adopts a flexible anion hybrid ultramicropore material to selectively adsorb xenon in xenon/krypton mixed gas, so as to realize the separation of xenon and krypton;
the fluorine-containing material with flexible functionThe general structural formula of the anion hybrid ultramicropore material is M- (C)12H8N2)-AF6Or M- (C)10H8N2S2)-AF6；
Wherein, C12H8N2Is an organic ligand 1, 2-dipyridyl acetylene, C10H8N2S2Is an organic ligand 4, 4' -dipyridyl disulfide, M is a metal ion, AF6Is an inorganic fluorine-containing anion.
The structural formula of the organic ligand 1, 2-dipyridyl acetylene is as follows:
Figure BDA0002130346770000021
the structural formula of the organic ligand 4, 4' -dipyridyl disulfide is as follows:
Figure BDA0002130346770000022
the flexible fluorine-containing anion hybrid ultramicropore material can show different stimulus responses to xenon/krypton molecules due to certain flexibility of a ligand, so that gas molecules with different properties can be effectively identified, and gas separation is realized.
The three-dimensional structure of the fluorine-containing anion hybrid ultramicropore material with the flexible function is shown as the following formula (I) or (II):
Figure BDA0002130346770000031
wherein, formula (I) represents M- (C)12H8N2)-AF6Structure, L1 is an organic ligand C12H8N2(ii) a Formula (II) represents M- (C)10H8N2S2)-AF6Structure, L2 is an organic ligand C10H8N2S2。
The pyridine rings in L1 and L2 have certain flexibility and can rotate.
Preferably, theM is selected from Cu2+、Zn2+、Co2+Or Ni2+。
Preferably, the AF is6Is NbF6 -、ZrF6 2-、GeF6 2-、SiF6 2-Or TiF6 2-。
The invention realizes the precise regulation and control of the pore diameter of the flexible functional fluorine-containing anion hybrid ultramicropore material by changing the types of inorganic fluorine-containing anions and metal ions, and modifies the chemical environment in the pore channel. Because the polarity of xenon molecules is obviously higher than that of krypton molecules, strong interaction force is generated between the xenon molecules and the ultramicropore material, and simultaneously, because the pyridine ring in the ligand has rotation adjustability, when the pyridine ring contacts xenon, the pyridine ring deflects and is converted to increase the pore diameter, so that the xenon is allowed to enter the pores. In addition, as the surface of the pore channel is distributed with high-density fluorine-containing anions, the acting force of the material and xenon is further enhanced, so that the xenon adsorption capacity is extremely high; and the action force of krypton molecules with small polarity and the material is too weak, so that the pyridine ring cannot rotate, and exclusion of krypton molecules is realized. Therefore, the ultramicropore material has very high xenon adsorption capacity and adsorption separation selectivity, and has very good application prospect when being used as an adsorbent in the field of xenon krypton separation.
In the present invention, the inorganic fluorine-containing anion AF6Metal ion M and organic ligand 1, 2-dipyridyl acetylene (C)12H8N2) The structural unit of the flexible functional fluorine-containing anion hybrid ultramicropore material constructed by coordination bonds is shown in figure 1, and has a one-dimensional pipeline type pore structure, wherein
Figure BDA0002130346770000041
Is an inorganic anion, and the anion is an inorganic anion,
Figure BDA0002130346770000042
is a metal ion, and is a metal ion,
Figure BDA0002130346770000043
is an organic ligand 1, 2-dipyridyl acetylene (C)12H8N2)。
In a preferred embodiment, the inorganic fluorine-containing anion is NbF6 -Organic ligand is 1, 2-dipyridyl acetylene, metal ion is Cu2+The composite fluorine-containing anion hybrid ultramicropore material with the flexible function is NbFSIX-2-Cu-i. NbFSIX-2-Cu-i has an adsorption capacity of 4.95mmol/g for xenon under the conditions of 1bar and 273K, almost no adsorption for krypton, and can separate xenon with purity of 95% -99.99% and krypton with purity of 98% -99.99% from xenon/krypton mixed gas.
In another preferred embodiment, the inorganic fluorine-containing anion is ZrF6 2-Organic ligand is 1, 2-dipyridyl acetylene, metal ion is Zn2+The prepared fluorine-containing anion hybrid ultramicropore material with the flexible function can separate xenon with the purity of 80-99 percent and krypton gas with the purity of 85-99.9 percent from xenon/krypton mixed gas.
Preferably, the mole percentage of xenon in the xenon/krypton gas mixture is 10-30%. The purity of krypton gas with the purity of more than 99.99 percent and xenon gas with the purity of 99.99 percent can be separated under the gas composition.
The xenon krypton gas separation method specifically comprises the following steps:
(1) adsorption: under the set adsorption temperature and adsorption pressure, introducing xenon/krypton mixed gas into an adsorption column filled with an adsorbent, adsorbing xenon by the adsorbent, penetrating krypton through the adsorption column, and obtaining high-purity krypton gas at an outlet of the adsorption column;
(2) desorption: stopping introducing the mixed gas after the xenon penetrates through the adsorption column, introducing inert gas for purging or heating desorption or vacuum desorption to treat the adsorption column, and desorbing the xenon from the adsorbent to obtain high-purity xenon gas;
the adsorbent is a fluoride-containing anion hybrid ultramicropore material with a flexible function.
Preferably, the adsorption temperature is-30 to 100 ℃, and more preferably 0 to 25 ℃, and the separation effect is optimal in the adsorption temperature range.
Preferably, the adsorption pressure is 0 to 10bar, more preferably 0.5 to 2bar, and the separation effect is optimal in the adsorption pressure range.
In the step (2), the temperature for temperature rise desorption is preferably 0 to 160 ℃, and more preferably 25 to 50 ℃.
Preferably, the pressure of the vacuum desorption is 0 to 1bar, and more preferably 0 to 0.2 bar.
Compared with the prior art, the invention has the main advantages that:
(1) the method for adsorbing and separating xenon and krypton by using the fluorine-containing anion hybrid ultramicropore material with the flexible function is provided, the strong acting force on xenon is shown by precisely regulating and controlling the pore diameter of the anion hybrid ultramicropore material and modifying the chemical environment in the pore, and meanwhile, the xenon enters the pore structure by controlling the rotation degree of a pyridine ring, so that the krypton is excluded, and the separation of the xenon and krypton is realized.
(2) Compared with the conventional adsorbent, the fluoride anion hybrid ultramicropore material with the flexible function has the advantages of adjustable pore structure, adjustable action force with adsorbate molecules and the like, and simultaneously has high adsorption capacity and high selectivity.
(3) The method can obtain high-purity xenon and krypton with the maximum of 99.999 percent.
(4) Compared with the extraction rectification and precision rectification technologies, the separation method provided by the invention has the outstanding advantages of low energy consumption, small equipment investment and the like.
(5) The anion hybrid ultramicropore material adsorbent is simple in preparation method, easy to regenerate, reusable and long in service life. The method has low energy consumption and low cost, and is suitable for industrialization.
Drawings
FIG. 1 shows a reaction mixture of an inorganic fluorine-containing anion AF6Metal ion M and organic ligand 1, 2-dipyridyl acetylene (C)12H8N2) A schematic structural unit diagram of a fluorine-containing anion hybrid ultramicropore material with a flexible function constructed by coordinate bonds;
FIG. 2 is the adsorption isotherm of the anion-hybridized ultramicropore material NbFSIX-2-Cu-i obtained in example 1 at 273K for xenon and krypton;
FIG. 3 is the adsorption isotherm of the anion-hybridized ultramicropore material NbFSIX-2-Cu-i obtained in example 1 at 298K for xenon and krypton;
FIG. 4 is a graph showing the transmittance of the anion-hybrid ultramicropore material NbFSIX-2-Cu-i obtained in example 1 at 273K for a mixed gas of xenon and krypton;
FIG. 5 is a graph showing the desorption curve of the anion-hybridized ultramicropore material NbFSIX-2-Cu-i obtained in example 1 at 298K;
FIG. 6 is the adsorption isotherm of the anion-hybridized ultramicropore material ZrFSIX-2-Zn-i obtained in example 2 for xenon and krypton at 273K;
FIG. 7 is the adsorption isotherm of the anion-hybridized ultramicropore material ZrFSIX-2-Cu-i obtained in example 3 for xenon and krypton at 273K.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
1mmol of Cu (BF)4)2、1mmol KNbF6Dissolving in 10mL of water, dissolving 1.5mmol of 1, 2-dipyridyl acetylene in 10mL of methanol, mixing the two solutions, stirring at room temperature for 24h, filtering the obtained slurry, and activating at room temperature under a vacuum condition for 24h to obtain the NbFSIX-2-Cu-i material.
The adsorption isotherms of the NbFSIX-2-Cu-i material at 273K and 298K for a single component of xenon and krypton were measured and are shown in FIGS. 2 and 3, respectively.
The obtained NbFSIX-2-Cu-i material is filled into a 5cm adsorption column, 0.1MPa xenon/krypton (molar ratio of 20: 80) mixed gas is introduced into the adsorption column at 0 ℃ at 3.5mL/min, high-purity krypton (more than 99.9%) gas can be obtained from the effluent gas, and adsorption is stopped when xenon penetrates. Then nitrogen is switched to purge the adsorption column at room temperature, the flow rate is 3.0mL/min, high-purity xenon (the purity is more than 99.9%) can be obtained, and the adsorption column can be recycled.
The penetration curve of NbFSIX-2-Cu-i material at 273K for the mixed gas of xenon and krypton is shown in FIG. 4.
The desorption curve of the NbFSIX-2-Cu-i material at 298K is shown in FIG. 5.
Example 2
1mmol of ZnZrF6Dissolving in 10mL of methanol, dissolving 1.5mmol of 1, 2-dipyridyl acetylene in 10mL of methanol, mixing the two solutions, stirring at room temperature for 24h, filtering the obtained slurry, and activating at room temperature under a vacuum condition for 24h to obtain the ZrFSIX-2-Zn-i material.
The adsorption isotherm of the ZrFSIX-2-Zn-i material at 273K for a single component of xenon and krypton is measured, and the result is shown in FIG. 6.
The ZrFSIX-2-Zn-i material is filled into a 5cm adsorption column, xenon/krypton (molar ratio of 20: 80) mixed gas with 0.1MPa is introduced into the adsorption column at 0 ℃ at 3.5mL/min, high-purity krypton (more than 99.9%) gas can be obtained from effluent gas, and adsorption is stopped when xenon penetrates through the gas. The adsorption column is purged by nitrogen at room temperature to obtain high-purity xenon (the purity is more than 90%), and the adsorption column can be recycled.
Example 3
1mmol of CuZrF6Dissolving in 10mL of methanol, dissolving 1.5mmol of 1, 2-dipyridyl acetylene in 10mL of methanol, mixing the two solutions, stirring at room temperature for 24h, filtering the obtained slurry, and activating at room temperature under a vacuum condition for 24h to obtain the ZrFSIX-2-Cu-i material.
Measuring the adsorption isotherm of the ZrFSIX-2-Cu-i material at 273K on a single component of xenon and krypton, and the result is shown in FIG. 7;
the ZrFSIX-2-Cu-i material is filled into a 5cm adsorption column, xenon/krypton (molar ratio of 20: 80) mixed gas with 0.1MPa is introduced into the adsorption column at 0 ℃ at 3.5mL/min, high-purity krypton (more than 99.9%) gas can be obtained from effluent gas, and adsorption is stopped when xenon penetrates through the gas. The adsorption column is purged by nitrogen at room temperature to obtain high-purity xenon (the purity is more than 85%), and the adsorption column can be recycled.
Example 4
1mmol of Cu (BF)4)2、1mmol(NH4)2SiF6Dissolving in 10mL of water, dissolving 1.5mmol of 1, 2-dipyridyl acetylene in 10mL of methanol, mixing the two solutions, stirring at 80 ℃ for 12h, carrying out suction filtration on the obtained slurry, and activating at 80 ℃ for 24h under a vacuum condition to obtain the SIFS-2-Cu-i material.
The adsorption isotherms of the SIFSIX-2-Cu-i material at 273K and 298K for single components of xenon and krypton were measured.
The obtained SIFSIX-2-Cu-i material is filled into a 5cm adsorption column, 0.1MPa xenon/krypton (molar ratio of 20: 80) mixed gas is introduced into the adsorption column at 0 ℃ at the speed of 3.5mL/min, high-purity krypton (more than 99.9%) gas can be obtained from the effluent gas, and adsorption is stopped when xenon penetrates. The adsorption column is purged by nitrogen at room temperature to obtain high-purity xenon (the purity is more than 80%), and the adsorption column can be recycled.
Example 5
1mmol of Cu (BF)4)2、1mmol(NH4)2GeF6Dissolving in 10mL of water, dissolving 1.5mmol of 1, 2-dipyridyl acetylene in 10mL of methanol, mixing the two solutions, stirring at 80 ℃ for 12h, carrying out suction filtration on the obtained slurry, and activating at 80 ℃ for 24h under a vacuum condition to obtain the GeFSIX-2-Cu-i material.
The absorption isotherms of the GeFSIX-2-Cu-i material at 273K, 298K for a single component of xenon or krypton were measured.
The GeFSIX-2-Cu-i material is filled into a 5cm adsorption column, 0.1MPa of xenon/krypton (molar ratio of 20: 80) mixed gas is introduced into the adsorption column at 0 ℃ at the rate of 3.5mL/min, high-purity krypton (more than 99.9%) gas can be obtained from the effluent gas, and adsorption is stopped when xenon penetrates. The adsorption column is purged by nitrogen at room temperature to obtain high-purity xenon (the purity is more than 85%), and the adsorption column can be recycled.
Example 6
1mmol of Cu (BF)4)2、1mmol(NH4)2TiF6Dissolving in 10mL of water, dissolving 1.5mmol of 1, 2-dipyridyl acetylene in 10mL of methanol, mixing the two solutions, stirring at 80 ℃ for 12h, carrying out suction filtration on the obtained slurry, and activating at 80 ℃ for 24h under a vacuum condition to obtain the TiFSIX-2-Cu-i material.
The adsorption isotherms of the TiFSIX-2-Cu-i material at 273K and 298K for single components of xenon and krypton were measured.
The TiFSIX-2-Cu-i material is filled into a 5cm adsorption column, 0.1MPa of xenon/krypton (molar ratio of 20: 80) mixed gas is introduced into the adsorption column at 0 ℃ at 3.5mL/min, high-purity krypton (more than 99.9%) gas can be obtained from the effluent gas, and adsorption is stopped when xenon penetrates. The adsorption column is purged by nitrogen at room temperature to obtain high-purity xenon (the purity is more than 80%), and the adsorption column can be recycled.
Example 7
0.5mmol of Cu (BF)4)2、1mmol(NH4)2GeF6Dissolving in 10mL of water, dissolving 1mmol of 4, 4' -dipyridyl disulfide in 20mL of methanol, mixing the two solutions, stirring at room temperature for 24h, carrying out suction filtration on the obtained slurry, and activating at 80 ℃ for 24h under a vacuum condition to obtain the GeFSIX-S-Cu-i material.
The absorption isotherms of the GeFSIX-S-Cu-i material at 273K, 298K for a single component of xenon or krypton were measured.
The GeFSIX-S-Cu-i material is filled into a 5cm adsorption column, 0.1MPa of xenon/krypton (molar ratio of 20: 80) mixed gas is introduced into the adsorption column at 0 ℃ at the rate of 3.5mL/min, high-purity krypton (more than 99.9%) gas can be obtained from the effluent gas, and adsorption is stopped when xenon penetrates. The adsorption column is purged by nitrogen at room temperature to obtain high-purity xenon (the purity is more than 80%), and the adsorption column can be recycled.
Example 8
0.5mmol of CuZrF6Dissolving in 20mL of methanol, dissolving 1mmol of 4, 4' -dipyridyl disulfide in 20mL of methanol, mixing the two solutions, stirring at room temperature for 24h, carrying out suction filtration on the obtained slurry, and activating at 80 ℃ for 24h under a vacuum condition to obtain the ZrFSIX-S-Cu-i material.
The adsorption isotherms of the ZrFSIX-S-Cu-i material at 273K and 298K for single components of xenon and krypton gas were measured.
The ZrFSIX-S-Cu-i material is filled into a 5cm adsorption column, xenon/krypton (molar ratio of 20: 80) mixed gas with 0.1MPa is introduced into the adsorption column at 0 ℃ at 3.5mL/min, high-purity krypton (more than 99.9%) gas can be obtained from effluent gas, and adsorption is stopped when xenon penetrates through the gas. The adsorption column is purged by nitrogen at room temperature to obtain high-purity xenon (the purity is more than 85%), and the adsorption column can be recycled.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (8)

1. A separation method of xenon and krypton is characterized in that a fluorine-containing anion hybrid ultramicropore material with a flexible function is adopted to selectively adsorb xenon in a xenon/krypton mixed gas, so that the separation of xenon and krypton is realized;
the general structural formula of the fluoride-containing anion hybrid ultramicropore material with the flexible function is M- (C)12H8N2)-AF6Or M- (C)10H8N2S2)-AF6The corresponding three-dimensional structures are respectively shown as formulas (I) and (II):
Figure FDA0002721928520000011
wherein, formula (I) represents M- (C)12H8N2)-AF6Structure, formula (II) represents M- (C)10H8N2S2)-AF6Structure;
l1 represents C12H8N2Is an organic ligand 1, 2-dipyridyl acetylene;
l2 represents C10H8N2S2Is an organic ligand, 4' -bipyridyl disulfide;
m is a metal ion selected from Cu2+、Zn2+、Co2+Or Ni2+；
AF6Is an inorganic fluorine-containing anion, is NbF6 -、ZrF6 2-、GeF6 2-、SiF6 2-Or TiF6 2-。
2. Xenon gas according to claim 1Krypton gas separation process, characterized in that the inorganic fluorine-containing anion is NbF6 -Organic ligand is 1, 2-dipyridyl acetylene, metal ion is Cu2+。
3. The method for separating xenon krypton as in claim 1, wherein the inorganic fluorine-containing anion is ZrF6 2-Organic ligand is 1, 2-dipyridyl acetylene, metal ion is Zn2+。
4. The method for separating krypton xenon from krypton according to any one of claims 1 to 3, wherein the method for separating krypton comprises:
(1) adsorption: under the set adsorption temperature and adsorption pressure, introducing xenon/krypton mixed gas into an adsorption column filled with an adsorbent, adsorbing xenon by the adsorbent, penetrating krypton through the adsorption column, and obtaining high-purity krypton gas at an outlet of the adsorption column;
(2) desorption: stopping introducing the mixed gas after the xenon penetrates through the adsorption column, introducing inert gas for purging or heating desorption or vacuum desorption to treat the adsorption column, and desorbing the xenon from the adsorbent to obtain high-purity xenon gas;
the adsorbent is a fluoride-containing anion hybrid ultramicropore material with a flexible function.
5. The method for separating krypton xenon from gas as claimed in claim 4, wherein in the step (1), the adsorption temperature is-30 to 100 ℃.
6. The method for separating krypton xenon from gas as claimed in claim 4, wherein in step (1), the adsorption pressure is 0-10 bar.
7. The method for separating krypton xenon from gas as claimed in claim 4, wherein in the step (2), the temperature for the temperature-rising desorption is 0-160 ℃.
8. The method for separating krypton xenon from gas as claimed in claim 4, wherein in step (2), the pressure of the vacuum desorption is 0-1 bar.
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