CN114621050B - Method for removing fluorine-containing olefin in hexafluorobutadiene - Google Patents
Method for removing fluorine-containing olefin in hexafluorobutadiene Download PDFInfo
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- CN114621050B CN114621050B CN202011454874.6A CN202011454874A CN114621050B CN 114621050 B CN114621050 B CN 114621050B CN 202011454874 A CN202011454874 A CN 202011454874A CN 114621050 B CN114621050 B CN 114621050B
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- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 25
- 229910052731 fluorine Inorganic materials 0.000 title claims description 25
- 239000011737 fluorine Substances 0.000 title claims description 25
- 150000001336 alkenes Chemical class 0.000 title claims description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 39
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000003463 adsorbent Substances 0.000 claims abstract description 12
- 125000000383 tetramethylene group Chemical class [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- 150000001879 copper Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 230000035515 penetration Effects 0.000 description 11
- 239000012535 impurity Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- WFOIWBGKCSYBJN-UHFFFAOYSA-N 1-fluorobut-1-ene Chemical class CCC=CF WFOIWBGKCSYBJN-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DXPCVBMFVUHPOU-UHFFFAOYSA-N 1,3,3,4,4,4-hexafluorobut-1-yne Chemical compound FC#CC(F)(F)C(F)(F)F DXPCVBMFVUHPOU-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- -1 boron oxide compound Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- 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
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- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- 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
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- 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
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Abstract
The invention discloses a method for removing fluoroolefins in hexafluorobutadiene, which comprises the following steps: adopting a graphene oxide doped HKUST-1 adsorption material as an adsorbent, and performing adsorption at 20-100 ℃ for 40h ‑1 ～200h ‑1 Is passed over a hexafluorobutadiene gas comprising a fluoroolefin comprising butadiene fluorochloride and/or a fluorinated butene dimer. The invention has the advantages of large adsorption capacity, mild adsorption condition, low equipment requirement and the like.
Description
Technical Field
The invention relates to the field of fluoridation, in particular to a method for removing fluoroolefins in hexafluorobutadiene by using a graphene oxide doped HKUST-1 adsorption material as an adsorbent.
Background
An electronic gas is an important branch of special gas, is an indispensable raw material in electronic industry production, and is widely applied to semiconductor processes such as thin film, etching, doping, vapor deposition, diffusion and the like. With the increasing environmental demands of people, the use of traditional fluorine-containing electronic gases in the future is greatly restricted. Hexafluorobutadiene is used as a new generation of electronic gas, the atmospheric lifetime is short (only 1.9 days), ODP is 0, GWP (100) is 0, and compared with the traditional etching gas, the hexafluorobutadiene has higher selectivity, can replace saturated fluorocarbon etching gas, and has high added value and market prospect.
When hexafluorobutadiene is used as etching gas in the semiconductor field, the purity of hexafluorobutadiene is required to be more than 99.9%. The hexafluorobutadiene prepared by different processes has different impurities and generally contains butadiene fluorochloride, fluorinated butene dimer and H 2 O, HF, small amounts of alcohols, etc. In order to improve the purity of hexafluorobutadiene, it is generally practiced in industry to purify it by a rectification method, and most of impurities can be removed by rectification, but azeotropic fluoroolefin compounds such as butadiene fluorochloride and fluorobutene dimer cannot be removed.
In order to remove azeotropic fluorine-containing olefin impurities, three methods of extractive distillation, chemical conversion and adsorption are generally adopted. The azeotropic distillation can be removed by extraction and rectification, but new impurities can be introduced, the production cost is increased, and the process is complex; the chemical conversion method has complex process and is easy to react the hexafluorobutadiene so as to reduce the yield; the adsorption method has low cost, convenient operation and mild adsorption condition, and is the most ideal purification method. The most central of the adsorption method is the development of an adsorbent, and the commonly used adsorbents for removing azeotropic fluorine-containing olefins at present comprise:
(1) Activated carbon. Japanese ONO H et al disclose a method for purifying crude hexafluorobutadiene with activated carbon having a particle size of 0.1 to 5mm and activated at 200℃for 5 hours or more under a He atmosphere of 1L/min to obtain a volume fraction of impurities of < 1X 10 -6 Is a purified hexafluorobutadiene of (a). However, the adsorption capacity of the activated carbon to fluorine-containing olefin is very small in the method, and the requirement of industrial production is difficult to meet.
(2) Molecular sieves. Steven a K et al, U.S. air chemicals, disclose a process for removing impurities such as water, alcohols, HF and other fluoroolefins from hexafluorobutadiene using a 5A molecular sieve. According to the method, the purpose of screening is achieved by utilizing different diameters of hexafluorobutadiene and impurity molecules, the removal of impurities such as water, alcohol and HF is more effective, but the molecular diameters of other fluoroolefin molecules (fluoroolefins such as butadiene fluorochloride, fluorobutene dimer and the like) are close to those of hexafluorobutadiene, so that the adsorption capacity of the molecular sieve on fluoroolefin impurities is very small.
(3) An oxide. Steven a K, air chemical company, U.S. discloses the use of A1 2 O 3 A method for purifying hexafluorobutadiene. However, in the purification process, adsorption releases heat, so that nucleophilic rearrangement reaction of hexafluorobutadiene is easy to generate hexafluorobutyne, and the temperature and pressure of the system rise rapidly, so that obvious potential safety hazards exist.
U.S. MASAHIRO Nakamura et al disclose a process for purifying crude hexafluorobutadiene using a boron oxide compound that uses boron oxide to obtain hexafluorobutadiene in purities as high as 99.999%. However, boron oxide is extremely hygroscopic and H as the adsorption reaction proceeds 2 O occupies adsorption sites, adsorption performance is rapidly reduced, and industrialization implementation is difficult.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for removing fluoroolefins in hexafluorobutadiene, which has the advantages of large adsorption capacity, mild adsorption conditions and low equipment requirements.
The invention aims at realizing the following technical scheme:
a process for removing fluoroolefins from hexafluorobutadiene, said process comprising:
adopting a graphene oxide doped HKUST-1 adsorption material as an adsorbent, and performing adsorption at 20-100 ℃ for 40h -1 ～200h -1 Is passed over a hexafluorobutadiene gas comprising a fluoroolefin comprising butadiene fluorochloride and/or a fluorinated butene dimer.
Preferably, the HKUST-1 adsorption material doped with graphene oxide is used as an adsorbent, and the adsorption temperature is 20-60 ℃ for 40h -1 ～120h -1 Is passed through hexafluoro comprising a fluoroolefinButadiene gas.
The adsorption temperature, the gas space velocity, the concentration of fluorine-containing olefin and the like can have great influence on the adsorption effect. Therefore:
further, the concentration of the fluorine-containing olefin is 100ppm to 1000ppm, and preferably the concentration of the fluorine-containing olefin is 100ppm to 300ppm.
Further, the pore diameter of the HKUST-1 adsorbing material doped with the graphene oxide is 0.5 nm-5.0 nm, the porosity is 85% -99%, and the specific surface area is 800m 2 /g～1500m 2 /g。
In order to further improve the removal effect of the fluorine-containing olefin in the hexafluorobutadiene, the HKUST-1 adsorption material doped with the graphene oxide is used after being activated at 150-500 ℃, and preferably, the activation temperature is 150-200 ℃.
The HKUST-1 adsorption material doped with graphene oxide is prepared by self, preferably by a solvothermal synthesis method, and comprises the following specific steps:
mixing 1,3, 5-benzene tricarboxylic acid, copper salt and graphene oxide in an organic solvent, heating at 100-250 ℃ for 12-48 hours, and performing post-treatment to obtain the graphene oxide doped HKUST-1 adsorption material. Preferably, the HKUST-1 adsorbing material doped with graphene oxide is obtained by heating for 24-48 h at 100-150 ℃ and then post-treating.
Further, the organic solvent is at least one selected from ethanol, DMF and n-propanol.
Further, the copper salt is at least one selected from copper acetate, copper nitrate and copper chloride.
Further, the post-processing step includes: and cooling to room temperature after the reaction is finished, and centrifugally separating to obtain a crude product, and washing and drying the crude product to obtain the graphene oxide doped HKUST-1 adsorption material.
The proportion of the raw materials 1,3, 5-benzene tricarboxylic acid, copper salt and graphene oxide has a great influence on the adsorption capacity of the prepared adsorption material. Therefore:
preferably, the mass ratio of the 1,3, 5-benzene tricarboxylic acid, the copper salt and the graphene oxide is as follows: 1:2: (1-10). More preferably, the mass ratio of the 1,3, 5-benzene tricarboxylic acid, the copper salt and the graphene oxide is 1:2: (1-5).
The HKUST-1 adsorption material doped with graphene oxide prepared by the invention has good adsorption performance on fluorine-containing olefins such as butadiene fluorochloride, fluorine-containing butene dimer and the like in hexafluorobutadiene, and the specific reason is that:
the HKUST-1 adsorbing material doped with graphene oxide prepared by the method has the pore diameter of 0.5-5.0 nm, has a mesoporous structure, can load more active components, and improves the adsorption capacity of the adsorbing material on fluorine-containing olefin (butadiene fluorochloride and fluorine-containing butene dimer);
the HKUST-1 adsorption material doped with graphene oxide, which is obtained by the invention, has high porosity and high specific surface area, and simultaneously has a mesoporous structure and a microporous structure, thereby being beneficial to the fluorine-containing olefin (butadiene fluorochloride and fluorine-containing butene dimer) to enter the mesopores without barriers and be fully contacted and adsorbed in the micropores.
The HKUST-1 adsorption material doped with graphene oxide has excellent mechanical stability and thermal stability, the activation temperature is increased, and more Cu is contained in the adsorption material 2+ Is reduced to Cu + Pi complexation with fluorine-containing olefin is carried out, and the adsorption capacity of the fluorine-containing olefin is further improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the HKUST-1 adsorption material doped with graphene oxide has high porosity and high specific surface area, and simultaneously has a mesoporous structure and a microporous structure, so that the adsorption capacity of fluorine-containing olefins such as butadiene fluorochloride, fluorine-containing butene dimer and the like is improved.
2. The HKUST-1 adsorption material doped with graphene oxide has improved mechanical stability and thermal stability, and has more Cu after activation + The adsorption capacity of the catalyst to fluorine-containing olefins such as butadiene fluorochloride and fluorine-containing butene dimer is improved.
3. The invention has the advantages of low adsorption temperature, mild condition, low requirement on adsorption equipment and convenient operation, and is suitable for industrialized production.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the invention to these specific embodiments. It will be appreciated by those skilled in the art that the invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Preparation example 1
The preparation of the graphene oxide doped HKUST-1 adsorption material comprises the following steps:
1g of 1,3, 5-benzene tricarboxylic acid, 2g of Cu (NO) were weighed out 3 ) 2 And 5g of graphene oxide are dissolved in ethanol, and are mixed and stirred until uniform. Heated at 150℃for 24h. And cooling to room temperature after the reaction is finished, and finally, vacuum drying at 120 ℃ to obtain the graphene oxide doped HKUST-1 adsorption material, which is marked as 1#HKUST-1.
PREPARATION EXAMPLES 2 to 5
The operation of this preparation example is identical to that of preparation example 1, except that: the mass of the added graphene oxide is 1g, 3g, 7g and 10g respectively, and the prepared adsorption materials are marked as 2#HKUST-1, 3#HKUST-1, 4#HKUST-1 and 5#HKUST-1.
Preparation examples 6 to 7
The operation of this preparation example is identical to that of preparation example 1, except that: the organic solvent adopts DMF and n-propanol respectively, and the prepared adsorption materials are marked as 6#HKUST-1 and 7#HKUST-1.
Preparation examples 8 to 9
The operation of this preparation example is identical to that of preparation example 1, except that: the copper salt is copper acetate and copper chloride respectively, and the prepared adsorption materials are marked as 8#HKUST-1 and 9#HKUST-1.
Preparation examples 10 to 12
The operation of this preparation example is identical to that of preparation example 1, except that: the reaction temperatures were respectively selected at 100deg.C, 200deg.C and 250deg.C, and the prepared adsorption materials were designated 10#HKUST-1, 11#HKUST-1 and 12#HKUST-1.
Example 1
Charging 5g 1# HKUST-1 into adsorption column, activating at 200deg.C, adsorbing at 60deg.C for 120 hr -1 Is passed through a space velocity zone containing a fluoroolefin (butadiene fluorochloride and fluorobutene)Dimer) having a concentration of 300ppm. And collecting hexafluorobutadiene gas after removing fluoroolefin at an outlet of the adsorption column for gas chromatography analysis, and calculating to obtain the penetrating adsorption capacity of butadiene fluorochloride and fluorinated butene dimer to be 1.23mL/g.
Examples 2 to 12
The operation of this embodiment is identical to that of embodiment 1, except that: the penetration adsorption capacities of butadiene fluorochloride and fluorinated butene dimer were calculated using 2#HKUST-1 to 12#HKUST-1 as the adsorption material for activation and adsorption, and the specific penetration adsorption capacities are shown in Table 1.
Comparative examples 1 to 3
The operation of this comparative example is the same as in example 1, except that: activated carbon, alumina and molecular sieve are used as adsorption materials for activation and adsorption respectively, and the penetration adsorption capacity of butadiene fluorochloride and fluorine-containing butene dimer is calculated and obtained, and the specific penetration adsorption capacity is shown in table 1.
TABLE 1 penetration adsorption capacities of different adsorbents
Examples 13 to 15
The operation of this embodiment is identical to that of embodiment 1, except that: 1# hkust-1 has an activation temperature of 150 ℃, 350 ℃, 500 ℃ respectively, and the breakthrough adsorption capacities of butadiene fluorochloride and fluorobutene dimer are calculated, and the specific breakthrough adsorption capacities are shown in table 2 below:
TABLE 2 penetration adsorption capacities of adsorbents at different activation temperatures
| Examples | Activation temperature/. Degree.C | Penetration adsorption capacity/mL/g |
| Example 13 | 150 | 1.08 |
| Example 14 | 350 | 0.54 |
| Example 15 | 500 | 0.31 |
Examples 16 to 19
The operation of this embodiment is identical to that of embodiment 1, except that: respectively for 40h -1 、80h -1 、160h -1 、200h -1 Is passed into hexafluorobutadiene gas containing fluoroolefins (butadiene fluorochloride and fluorinated butene dimer), and the breakthrough adsorption capacities of butadiene fluorochloride and fluorinated butene dimer are calculated, and are shown in the following table 3:
TABLE 3 penetration adsorption capacities of adsorbents at different airspeeds
| Examples | Airspeed/h -1 | Penetration adsorption capacity/mL/g |
| Example 16 | 40 | 1.15 |
| Example 17 | 80 | 1.01 |
| Example 18 | 160 | 0.77 |
| Example 19 | 200 | 0.61 |
Examples 20 to 23
The operation of this embodiment is identical to that of embodiment 1, except that: the adsorption temperatures were 20 ℃, 40 ℃, 80 ℃, 100 ℃ respectively, and the breakthrough adsorption capacities of butadiene fluorochloride and fluorobutene dimer were calculated, and the specific breakthrough adsorption capacities are shown in table 4 below:
TABLE 4 penetration adsorption Capacity of adsorbents at different adsorption temperatures
| Examples | Adsorption temperature/. Degree.C | Penetration adsorption capacity/mL/g |
| Example 20 | 20 | 0.99 |
| Example 21 | 40 | 1.12 |
| Example 22 | 80 | 0.73 |
| Example 23 | 100 | 0.57 |
Examples 24 to 27
The operation of this embodiment is identical to that of embodiment 1, except that: the concentration of fluoroolefins was 100ppm, 500ppm, 800ppm, 1000ppm, respectively, calculated as the breakthrough adsorption capacities for butadiene fluorochloride and fluorobutene dimer, the specific breakthrough adsorption capacities are shown in table 5 below:
TABLE 5 breakthrough adsorption capacities of adsorbents with different fluoroolefin concentrations
Claims (8)
1. A method for removing fluorine-containing olefin in hexafluorobutadiene, which is characterized in that: the method comprises the following steps:
adopting a graphene oxide doped HKUST-1 adsorption material as an adsorbent, and performing adsorption at 20-100 ℃ for 40h -1 ～200h -1 Is passed through a hexafluorobutadiene gas comprising a fluoroolefin comprising butadiene fluorochloride and/or a fluorinated butene dimer;
the pore diameter of the HKUST-1 adsorption material doped with graphene oxide is 0.5 nm-5.0 nm, the porosity is 85% -99%, and the specific surface area is 800m 2 /g～1500m 2 /g；
The HKUST-1 adsorbing material doped with graphene oxide is prepared by a solvothermal synthesis method and comprises the following steps:
mixing 1,3, 5-benzene tricarboxylic acid, copper salt and graphene oxide in an organic solvent, heating at 100-250 ℃ for 12-48 hours, and performing post-treatment to obtain the graphene oxide doped HKUST-1 adsorption material;
the mass ratio of the 1,3, 5-benzene tricarboxylic acid, the copper salt and the graphene oxide is 1:2: (1-7).
2. The method for removing fluoroolefins from hexafluorobutadiene according to claim 1, wherein: at the adsorption temperature of 20-60 ℃ for 40h -1 ～120h -1 Is passed through a hexafluorobutadiene gas comprising a fluoroolefin.
3. The method for removing fluoroolefins from hexafluorobutadiene according to claim 1 or 2, wherein: the concentration of the fluorine-containing olefin is 100ppm to 1000ppm.
4. The method for removing fluoroolefins from hexafluorobutadiene according to claim 1, wherein: the HKUST-1 adsorption material doped with the graphene oxide is used after being activated at 150-500 ℃.
5. The method for removing fluoroolefins from hexafluorobutadiene according to claim 1, wherein: the mass ratio of the 1,3, 5-benzene tricarboxylic acid, the copper salt and the graphene oxide is 1:2: (1-5).
6. The method for removing fluoroolefins from hexafluorobutadiene according to claim 1, wherein: the organic solvent is at least one selected from ethanol, DMF and n-propanol.
7. The method for removing fluoroolefins from hexafluorobutadiene according to claim 1, wherein: the copper salt is at least one selected from copper acetate, copper nitrate and copper chloride.
8. The method for removing fluoroolefins from hexafluorobutadiene according to claim 1, wherein: the post-treatment step comprises the following steps: and cooling to room temperature after the reaction is finished, and centrifugally separating to obtain a crude product, and washing and drying the crude product to obtain the graphene oxide doped HKUST-1 adsorption material.
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| US6544319B1 (en) * | 2002-01-16 | 2003-04-08 | Air Products And Chemicals, Inc. | Purification of hexafluoro-1,3-butadiene |
| CN106349008A (en) * | 2016-07-19 | 2017-01-25 | 浙江博瑞电子科技有限公司 | Method for purifying butadiene hexafluoride |
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| CN108440235A (en) * | 2018-03-27 | 2018-08-24 | 浙江大学 | A method of detaching 1,3- butadiene from four carbon hydrocarbon gaseous mixtures |
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| US6544319B1 (en) * | 2002-01-16 | 2003-04-08 | Air Products And Chemicals, Inc. | Purification of hexafluoro-1,3-butadiene |
| CN107032949A (en) * | 2016-02-04 | 2017-08-11 | 浙江蓝天环保高科技股份有限公司 | A kind of purification process of hexachlorobutadiene |
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