CN110451466A - A kind of xenon Krypton separation method - Google Patents
A kind of xenon Krypton separation method Download PDFInfo
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- CN110451466A CN110451466A CN201910635964.6A CN201910635964A CN110451466A CN 110451466 A CN110451466 A CN 110451466A CN 201910635964 A CN201910635964 A CN 201910635964A CN 110451466 A CN110451466 A CN 110451466A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
- B01J20/28097—Shape or type of pores, voids, channels, ducts being coated, filled or plugged with specific compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0052—Physical processing only by adsorption in solids
- C01B23/0057—Physical processing only by adsorption in solids characterised by the adsorbent
Abstract
The invention discloses a kind of xenon Krypton separation methods, selective absorption xenon, the separation of realization xenon and Krypton in xenon/Krypton gaseous mixture using the fluo anion hydridization ultra-microporous material with flexibility function；The general structure of the fluo anion hydridization ultra-microporous material with flexibility function is M- (C12H8N2)‑AF6Or M- (C10H8N2S2)‑AF6；Wherein, C12H8N2For organic ligand 1, bis- pyridine acetylene of 2-, C10H8N2S2For organic ligand 4,4'-Bipyridine disulfide, M is metal ion, AF6For inorganic fluo anion.The fluo anion hydridization ultra-microporous material with flexibility function of the present invention has pore structure adjustable, adjustable with adsorption molecule active force compared with common adsorbents, while having both high-adsorption-capacity and highly selective.
Description
Technical field
The present invention relates to gas separation technique fields, and in particular to a kind of xenon Krypton separation method.
Background technique
Inert gas xenon and Krypton are industrial gasses important in national economy, since it is with special physical
Matter has in fields such as electronics, medicine, electric light source, gas laser, plasma jet and semiconductors and is widely applied.Xenon and krypton
Gas is mainly derived from air, and content is extremely low, only 0.087ppmv and 1ppmv.And currently, with economic recovery, novel industry
The demand of xenon and Krypton will be significantly greatly increased by rapidly developing.
Currently, industrially mainly preparing high-purity xenon and Krypton by way of cryogenic rectification.In large-scale space division device
In, the high concentration mixture of xenon and Krypton is separated as by-product, and high-purity xenon and Krypton, need in order to obtain
Mixture is separated by cryogenic rectification.But since xenon and Krypton relative volatility are smaller, physical property is similar, so that traditional
Separate mode has the deficiencies of high energy consumption, at high cost, complex process, significantly limits their industrial application.Therefore, it needs
Efficient, energy-efficient isolation technics is developed, realizes the separation of xenon/Krypton.
In recent years, since low energy consumption, the advantages such as low with production cost easy to operate, the adsorption separation technology based on porous material
Gradually substituting traditional cryogenic rectification technology.The key of the technology is that exploitation has both high capacity and highly selective adsorbent
Material, but often there is high-adsorption-capacity and highly selective the phenomenon that can not getting both in existing sorbent material, seriously affected it
Industrial application value.
For example, traditional solid absorbent NaA molecular sieve is 20%~30% to the adsorption capacity of xenon, selectively it is only
For 4~6 (100kPa, 298K), lower adsorption capacity and selectivity limit they application (J.Chem.Phys, 1997,
107(11):4364-4372).For another example, a kind of porous organic molecule cage CC3 is used for the separation of xenon and Krypton, and CC3 is to xenon
Gas, Krypton adsorbance be respectively 2.42,0.92mmol/g (100kPa, 298K), the ratio between adsorbance only 2.63, separation selectivity
Low (Nature Materials, 2014,13 (10): 954-960).In addition, metal-organic framework material SBMOF-2 is to xenon table
Reveal stronger adsorption, so that the adsorption capacity of xenon rises to 2.83mmol/g (100kPa, 298K), but due to it
Still there is certain adsorbance (0.9mmol/g) to Krypton, limits its separation selectivity (Journal of the American
Chemical Society,2015,137(22):7007-7010)。
Therefore exploitation has both high capacity and highly selective sorbent material realizes that efficiently separating for xenon Krypton still has
There is larger challenge.
Summary of the invention
For shortcoming existing for this field, the present invention provides a kind of xenon Krypton separation methods, to have flexibility
The fluo anion hydridization ultra-microporous material of function is contacted with xenon/Krypton gaseous mixture, is selected xenon as adsorbent
Property identification capture, realize xenon and Krypton separation.
A kind of xenon Krypton separation method, using the fluo anion hydridization ultra-microporous material with flexibility function in xenon
Selective absorption xenon in gas/Krypton gaseous mixture realizes the separation of xenon and Krypton；
The general structure of the fluo anion hydridization ultra-microporous material with flexibility function is M- (C12H8N2)-AF6
Or M- (C10H8N2S2)-AF6；
Wherein, C12H8N2For organic ligand 1, bis- pyridine acetylene of 2-, C10H8N2S2For two sulphur of organic ligand 4,4 '-bipyridyl
Ether, M are metal ion, AF6For inorganic fluo anion.
The structural formula of the bis- pyridine acetylene of organic ligand 1,2- are as follows:
The structural formula of the organic ligand 4,4 '-bipyridyl disulfide are as follows:
The fluo anion hydridization ultra-microporous material with flexibility function due to its ligand have certain flexibility,
It can express to xenon/different stimuli responsive of Krypton molecule, therefore gas molecule of different nature can be efficiently identified, thus
Realize gas separation.
The three-dimensional structure such as following formula (I) or (II) of the fluo anion hydridization ultra-microporous material with flexibility function
It is shown:
Wherein, formula (I) represents M- (C12H8N2)-AF6Structure, L1 are organic ligand C12H8N2；Formula (II) represents M-
(C10H8N2S2)-AF6Structure, L2 are organic ligand C10H8N2S2。
Pyridine ring in the L1 and L2 has certain flexibility, can rotate.
Preferably, the M is selected from Cu2+、Zn2+、Co2+Or Ni2+。
Preferably, the AF6For NbF6 -、ZrF6 2-、GeF6 2-、SiF6 2-Or TiF6 2-。
The present invention realizes there is flexibility function fluo anion by changing inorganic fluo anion and species of metal ion
The control accurate in hydridization ultra-microporous material aperture, and chemical environment in its duct is modified.Due to the polarity of xenon molecule
It is significantly higher than Krypton molecule, generates strong interaction force with ultra-microporous material, simultaneously because the pyridine ring in ligand has
There is rotation portability, when contacting with xenon, pyridine ring, which deflects, turns hole diameter enlargement to allow in xenon access aperture.This
Outside, since highdensity fluo anion is distributed in channel surfaces, the active force of material and xenon is further enhanced, is caused high
Xenon adsorption capacity；And polarity it is small Krypton molecule and material effects power it is too weak, pyridine ring can not rotate, realize Krypton
The exclusion of molecule.Therefore, such ultra-microporous material has both very high xenon adsorption capacity and adsorbing separation selectivity, as xenon
The adsorbent of gas Krypton separation field has extraordinary application prospect.
In the present invention, by the inorganic fluo anion AF6, bis- pyridine acetylene of metal ions M and organic ligand 1,2-
(C12H8N2) pass through the structural unit of the built-up fluo anion hydridization ultra-microporous material with flexibility function of coordinate bond
As shown in Figure 1, there is one-dimensional duct type pore structure, whereinFor inorganic anion,For metal ion,For bis- pyridine acetylene (C of organic ligand 1,2-12H8N2)。
In a preferred example, the inorganic fluo anion is NbF6 -, organic ligand be bis- pyridine acetylene of 1,2-, metal
Ion is Cu2+, the fluo anion hydridization ultra-microporous material with flexibility function of composition is NbFSIX-2-Cu-i.NbFSIX-
2-Cu-i is up to 4.95mmol/g to the adsorption capacity of xenon under the conditions of 1bar, 273K, and hardly adsorbs to Krypton, can be from
It is 95%~99.99% xenon and 98%~99.99% Krypton gas that purity is isolated in xenon/Krypton gaseous mixture.
In another preferred example, the inorganic fluo anion is ZrF6 2-, organic ligand be bis- pyridine acetylene of 1,2-,
Metal ion is Zn2+, the fluo anion hydridization ultra-microporous material with flexibility function of composition can be from xenon/Krypton gaseous mixture
In isolate purity be 80%~99% xenon and 85%~99.9% Krypton gas.
Preferably, the molar percentage of xenon is 10%~30% in the xenon/Krypton gaseous mixture.This gas group
Purity be may separate out under greater than 99.99% Krypton and 99.99% xenon gas.
The xenon Krypton separation method specifically includes:
(1) it adsorbs: under setting adsorption temp, adsorptive pressure, xenon/Krypton gaseous mixture being passed through the suction equipped with adsorbent
In attached column, xenon is adsorbed by adsorbent, and Krypton penetrates adsorption column, and absorption column outlet obtains high-purity Krypton gas；
(2) be desorbed: after xenon penetrates adsorption column, stopping is passed through gaseous mixture, is passed through inert gas purge or heating desorption
Or vacuum desorption handles adsorption column, and xenon is solved adsorption desorption from adsorbent, obtains high-purity xenon gas；
The adsorbent is the fluo anion hydridization ultra-microporous material with flexibility function.
Preferably, the adsorption temp be -30~100 DEG C, further preferably 0~25 DEG C, in the adsorption temp
Under range, separating effect is best.
Preferably, the adsorptive pressure is 0~10bar, further preferably 0.5~2bar, in the adsorptive pressure
Under range, separating effect is best.
In step (2), preferably, the temperature of the heating desorption is 0~160 DEG C, further preferably 25~50 DEG C.
Preferably, the pressure of the vacuum desorption is 0~1bar, further preferably 0~0.2bar.
Compared with prior art, the present invention major advantage includes:
(1) a kind of side of fluo anion hydridization ultra-microporous material adsorbing separation xenon Krypton with flexibility function is provided
Method, by control accurate anion hydridization ultra-microporous material aperture and modification hole in chemical environment, make its to xenon show compared with
High forces, while by the degree of rotation of control pyridine ring, so that xenon enters in pore structure, and exclusion is carried out to Krypton,
Realize the separation to xenon Krypton.
(2) the fluo anion hydridization ultra-microporous material of the present invention with flexibility function and common adsorbents phase
Than it is adjustable, adjustable with adsorption molecule active force to have many advantages, such as pore structure, while having both high-adsorption-capacity and highly selective.
(3) xenon of high-purity, Krypton can be obtained in this method, reaches as high as 99.999%.
(4) present invention provide separation method compared with extracting rectifying and precise distillation technology, have low energy consumption, equipment investment
Outstanding advantages of small.
(5) anion hydridization ultra-microporous material sorbent preparation method of the present invention is simple, and easily regeneration, repeats
It utilizes, long service life.The method of the present invention low energy consumption, low cost are suitable for industrialization.
Detailed description of the invention
Fig. 1 is by inorganic fluo anion AF6, bis- pyridine acetylene (C of metal ions M and organic ligand 1,2-12H8N2) logical
Cross the structural unit schematic diagram of the built-up fluo anion hydridization ultra-microporous material with flexibility function of coordinate bond；
Fig. 2 is for 1 gained anion hydridization ultra-microporous material NbFSIX-2-Cu-i of embodiment to xenon, Krypton at 273K
Adsorption isotherm；
Fig. 3 is for 1 gained anion hydridization ultra-microporous material NbFSIX-2-Cu-i of embodiment in 298K to xenon, Krypton
Adsorption isotherm；
Fig. 4 is for 1 gained anion hydridization ultra-microporous material NbFSIX-2-Cu-i of embodiment in 273K to xenon/Krypton
The breakthrough curve of gaseous mixture；
Fig. 5 is 1 gained anion hydridization ultra-microporous material NbFSIX-2-Cu-i desorption curve in 298K of embodiment；
Fig. 6 is for 2 gained anion hydridization ultra-microporous material ZrFSIX-2-Zn-i of embodiment in 273K to xenon, Krypton
Adsorption isotherm；
Fig. 7 is for 3 gained anion hydridization ultra-microporous material ZrFSIX-2-Cu-i of embodiment in 273K to xenon, Krypton
Adsorption isotherm.
Specific embodiment
With reference to the accompanying drawing and specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate
The present invention rather than limit the scope of the invention.The operating method of actual conditions is not specified in the following example, usually according to
Normal condition, or according to the normal condition proposed by manufacturer.
Embodiment 1
By 1mmol Cu (BF4)2、1mmol KNbF6It is dissolved in 10mL water, 1,2-, the bis- pyridine acetylene of 1.5mmol is dissolved in
10mL methanol, the two mixed room temperature stir for 24 hours, and gained slurry activates for 24 hours under vacuumized conditions at room temperature after filtering, and obtain
NbFSIX-2-Cu-i material.
NbFSIX-2-Cu-i material is measured at 273K, 298K to the adsorption isotherm of xenon, the one pack system of Krypton, knot
Fruit difference is as shown in Figure 2,3.
Gained NbFSIX-2-Cu-i material is filled into 5cm adsorption column, xenon/Krypton of 0.1MPa (is rubbed at 0 DEG C
You are than 20:80) gaseous mixture with 3.5mL/min is passed through adsorption column, it can get high-purity Krypton (being greater than 99.9%) in eluting gas
Gas stops absorption when xenon penetrates.Switching nitrogen room temperature purges adsorption column afterwards, and height can be obtained in flow velocity 3.0mL/min
Pure xenon (purity is greater than 99.9%), adsorption column can be recycled.
NbFSIX-2-Cu-i material is as shown in Figure 4 to xenon/Krypton gaseous mixture breakthrough curve in 273K.
NbFSIX-2-Cu-i material desorption curve in 298K is as shown in Figure 5.
Embodiment 2
By 1mmol ZnZrF6It is dissolved in 10mL methanol, 1,2-, the bis- pyridine acetylene of 1.5mmol is dissolved in 10mL methanol, the two
Mixed room temperature stirs for 24 hours, and gained slurry activates for 24 hours under vacuumized conditions at room temperature after filtering, and obtains ZrFSIX-2-Zn-i material
Material.
ZrFSIX-2-Zn-i material is measured at 273K to the adsorption isotherm of xenon, the one pack system of Krypton, as a result as schemed
Shown in 6.
Gained ZrFSIX-2-Zn-i material is filled into 5cm adsorption column, xenon/Krypton of 0.1MPa (is rubbed at 0 DEG C
You are than 20:80) gaseous mixture with 3.5mL/min is passed through adsorption column, it can get high-purity Krypton (being greater than 99.9%) in eluting gas
Gas stops absorption when xenon penetrates.Adsorption column is purged using nitrogen room temperature, obtains high-purity xenon (purity is greater than 90%),
Adsorption column can be recycled.
Embodiment 3
By 1mmol CuZrF6It is dissolved in 10mL methanol, 1,2-, the bis- pyridine acetylene of 1.5mmol is dissolved in 10mL methanol, the two
Mixed room temperature stirs for 24 hours, and gained slurry activates for 24 hours under vacuumized conditions at room temperature after filtering, and obtains ZrFSIX-2-Cu-i material
Material.
ZrFSIX-2-Cu-i material is measured at 273K to the adsorption isotherm of xenon, the one pack system of Krypton, as a result as schemed
Shown in 7；
Gained ZrFSIX-2-Cu-i material is filled into 5cm adsorption column, xenon/Krypton of 0.1MPa (is rubbed at 0 DEG C
You are than 20:80) gaseous mixture with 3.5mL/min is passed through adsorption column, it can get high-purity Krypton (being greater than 99.9%) in eluting gas
Gas stops absorption when xenon penetrates.Adsorption column is purged using nitrogen room temperature, obtains high-purity xenon (purity is greater than 85%),
Adsorption column can be recycled.
Embodiment 4
By 1mmol Cu (BF4)2、1mmol(NH4)2SiF6It is dissolved in 10mL water, 1,2-, the bis- pyridine acetylene of 1.5mmol is molten
In 10mL methanol, the two mixes 80 DEG C of stirring 12h, activates for 24 hours, obtains under vacuumized conditions at 80 DEG C after gained slurry suction filtration
SIFSIX-2-Cu-i material.
SIFSIX-2-Cu-i material is measured at 273K, 298K to the adsorption isotherm of xenon, the one pack system of Krypton.
Gained SIFSIX-2-Cu-i material is filled into 5cm adsorption column, xenon/Krypton of 0.1MPa (is rubbed at 0 DEG C
You are than 20:80) gaseous mixture with 3.5mL/min is passed through adsorption column, it can get high-purity Krypton (being greater than 99.9%) in eluting gas
Gas stops absorption when xenon penetrates.Adsorption column is purged using nitrogen room temperature, obtains high-purity xenon (purity is greater than 80%),
Adsorption column can be recycled.
Embodiment 5
By 1mmol Cu (BF4)2、1mmol(NH4)2GeF6It is dissolved in 10mL water, 1,2-, the bis- pyridine acetylene of 1.5mmol is molten
In 10mL methanol, the two mixes 80 DEG C of stirring 12h, activates for 24 hours, obtains under vacuumized conditions at 80 DEG C after gained slurry suction filtration
GeFSIX-2-Cu-i material.
GeFSIX-2-Cu-i material is measured at 273K, 298K to the adsorption isotherm of xenon, the one pack system of Krypton.
Gained GeFSIX-2-Cu-i material is filled into 5cm adsorption column, xenon/Krypton of 0.1MPa (is rubbed at 0 DEG C
You are than 20:80) gaseous mixture with 3.5mL/min is passed through adsorption column, it can get high-purity Krypton (being greater than 99.9%) in eluting gas
Gas stops absorption when xenon penetrates.Adsorption column is purged using nitrogen room temperature, obtains high-purity xenon (purity is greater than 85%),
Adsorption column can be recycled.
Embodiment 6
By 1mmol Cu (BF4)2、1mmol(NH4)2TiF6It is dissolved in 10mL water, 1,2-, the bis- pyridine acetylene of 1.5mmol is molten
In 10mL methanol, the two mixes 80 DEG C of stirring 12h, activates for 24 hours, obtains under vacuumized conditions at 80 DEG C after gained slurry suction filtration
TiFSIX-2-Cu-i material.
TiFSIX-2-Cu-i material is measured at 273K, 298K to the adsorption isotherm of xenon, the one pack system of Krypton.
Gained TiFSIX-2-Cu-i material is filled into 5cm adsorption column, xenon/Krypton of 0.1MPa (is rubbed at 0 DEG C
You are than 20:80) gaseous mixture with 3.5mL/min is passed through adsorption column, it can get high-purity Krypton (being greater than 99.9%) in eluting gas
Gas stops absorption when xenon penetrates.Adsorption column is purged using nitrogen room temperature, obtains high-purity xenon (purity is greater than 80%),
Adsorption column can be recycled.
Embodiment 7
By 0.5mmol Cu (BF4)2、1mmol(NH4)2GeF6It is dissolved in 10mL water, by the 4,4'-Bipyridine disulfide of 1mmol
It is dissolved in 20mL methanol, the two mixed room temperature stirs for 24 hours, activates for 24 hours, obtains under vacuumized conditions at 80 DEG C after gained slurry suction filtration
GeFSIX-S-Cu-i material.
GeFSIX-S-Cu-i material is measured at 273K, 298K to the adsorption isotherm of xenon, the one pack system of Krypton.
Gained GeFSIX-S-Cu-i material is filled into 5cm adsorption column, xenon/Krypton of 0.1MPa (is rubbed at 0 DEG C
You are than 20:80) gaseous mixture with 3.5mL/min is passed through adsorption column, it can get high-purity Krypton (being greater than 99.9%) in eluting gas
Gas stops absorption when xenon penetrates.Adsorption column is purged using nitrogen room temperature, obtains high-purity xenon (purity is greater than 80%),
Adsorption column can be recycled.
Embodiment 8
By 0.5mmol CuZrF6It is dissolved in 20mL methanol, the 4,4'-Bipyridine disulfide of 1mmol is dissolved in 20mL methanol,
The two mixed room temperature stirs for 24 hours, activates for 24 hours under vacuumized conditions at 80 DEG C after gained slurry suction filtration, obtains ZrFSIX-S-Cu-i
Material.
ZrFSIX-S-Cu-i material is measured at 273K, 298K to the adsorption isotherm of xenon, the one pack system of Krypton.
Gained ZrFSIX-S-Cu-i material is filled into 5cm adsorption column, xenon/Krypton of 0.1MPa (is rubbed at 0 DEG C
You are than 20:80) gaseous mixture with 3.5mL/min is passed through adsorption column, it can get high-purity Krypton (being greater than 99.9%) in eluting gas
Gas stops absorption when xenon penetrates.Adsorption column is purged using nitrogen room temperature, obtains high-purity xenon (purity is greater than 85%),
Adsorption column can be recycled.
In addition, it should also be understood that, those skilled in the art can be to this hair after having read foregoing description content of the invention
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (10)
1. a kind of xenon Krypton separation method, which is characterized in that using the fluo anion hydridization ultramicropore with flexibility function
Material selective absorption xenon in xenon/Krypton gaseous mixture realizes the separation of xenon and Krypton；
The general structure of the fluo anion hydridization ultra-microporous material with flexibility function is M- (C12H8N2)-AF6Or M-
(C10H8N2S2)-AF6, corresponding three-dimensional structure is respectively as shown in formula (I), (II):
Wherein, formula (I) represents M- (C12H8N2)-AF6Structure, formula (II) represent M- (C10H8N2S2)-AF6Structure；
L1 represents C12H8N2, it is organic ligand 1, bis- pyridine acetylene of 2-；
L2 represents C10H8N2S2, it is organic ligand 4,4'-Bipyridine disulfide；
M is metal ion；
AF6For inorganic fluo anion.
2. xenon Krypton separation method according to claim 1, which is characterized in that the M is selected from Cu2+、Zn2+、Co2+Or
Ni2+。
3. xenon Krypton separation method according to claim 1, which is characterized in that the AF6For NbF6 -、ZrF6 2-、
GeF6 2-、SiF6 2-Or TiF6 2-。
4. xenon Krypton separation method according to claim 1, which is characterized in that the inorganic fluo anion is
NbF6 -, organic ligand be bis- pyridine acetylene of 1,2-, metal ion Cu2+。
5. xenon Krypton separation method according to claim 1, which is characterized in that the inorganic fluo anion is
ZrF6 2-, organic ligand be bis- pyridine acetylene of 1,2-, metal ion Zn2+。
6. xenon Krypton separation method described in any claim according to claim 1~5, which is characterized in that the xenon
Gas Krypton separation method specifically includes:
(1) it adsorbs: under setting adsorption temp, adsorptive pressure, xenon/Krypton gaseous mixture being passed through the adsorption column equipped with adsorbent
In, xenon is adsorbed by adsorbent, and Krypton penetrates adsorption column, and absorption column outlet obtains high-purity Krypton gas；
(2) be desorbed: after xenon penetrates adsorption column, stopping is passed through gaseous mixture, is passed through inert gas purge or heating desorption or true
Sky desorption processing adsorption column, solves adsorption desorption for xenon from adsorbent, obtains high-purity xenon gas；
The adsorbent is the fluo anion hydridization ultra-microporous material with flexibility function.
7. xenon Krypton separation method according to claim 6, which is characterized in that in step (1), the adsorption temp
It is -30~100 DEG C.
8. xenon Krypton separation method according to claim 6, which is characterized in that in step (1), the adsorptive pressure
For 0~10bar.
9. xenon Krypton separation method according to claim 6, which is characterized in that in step (2), the heating desorption
Temperature is 0~160 DEG C.
10. xenon Krypton separation method according to claim 6, which is characterized in that in step (2), the vacuum desorption
Pressure be 0~1bar.
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| US20110126708A1 (en) * | 2005-06-15 | 2011-06-02 | Rodriguez Navarro Jorge Andres | Gas Adsorbents Based on Microporous Coordination Polymers |
| CN105944680A (en) * | 2016-05-17 | 2016-09-21 | 浙江大学 | Method using absorption to separate propylene and propyne |
| CN108727607A (en) * | 2018-05-22 | 2018-11-02 | 浙江大学 | A kind of separation method for detaching the metal-organic framework material and xenon Krypton of xenon and Krypton |
| CN109153005A (en) * | 2016-02-02 | 2019-01-04 | 利默里克大学 | The method of gas separation |
-
2019
- 2019-07-15 CN CN201910635964.6A patent/CN110451466B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110126708A1 (en) * | 2005-06-15 | 2011-06-02 | Rodriguez Navarro Jorge Andres | Gas Adsorbents Based on Microporous Coordination Polymers |
| CN109153005A (en) * | 2016-02-02 | 2019-01-04 | 利默里克大学 | The method of gas separation |
| CN105944680A (en) * | 2016-05-17 | 2016-09-21 | 浙江大学 | Method using absorption to separate propylene and propyne |
| CN108727607A (en) * | 2018-05-22 | 2018-11-02 | 浙江大学 | A kind of separation method for detaching the metal-organic framework material and xenon Krypton of xenon and Krypton |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583244A (en) * | 2021-06-17 | 2021-11-02 | 浙江大学 | Metal organic framework material and preparation method and application thereof |
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