CN113842744B - Adsorption purification recycling method for perfluoro-isobutyronitrile/carbon dioxide recovered insulating gas - Google Patents
Adsorption purification recycling method for perfluoro-isobutyronitrile/carbon dioxide recovered insulating gas Download PDFInfo
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- CN113842744B CN113842744B CN202111037099.9A CN202111037099A CN113842744B CN 113842744 B CN113842744 B CN 113842744B CN 202111037099 A CN202111037099 A CN 202111037099A CN 113842744 B CN113842744 B CN 113842744B
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- perfluoroisobutyronitrile
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- carbon dioxide
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- AASDJASZOZGYMM-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile Chemical compound FC(F)(F)C(F)(C#N)C(F)(F)F AASDJASZOZGYMM-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 75
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 238000000746 purification Methods 0.000 title claims abstract description 11
- 239000003463 adsorbent Substances 0.000 claims abstract description 96
- 239000012535 impurity Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 238000011068 loading method Methods 0.000 claims description 27
- 239000002808 molecular sieve Substances 0.000 claims description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- -1 salt ion Chemical class 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
- SFFUEHODRAXXIA-UHFFFAOYSA-N 2,2,2-trifluoroacetonitrile Chemical compound FC(F)(F)C#N SFFUEHODRAXXIA-UHFFFAOYSA-N 0.000 claims description 2
- MTLOQUGSPBVZEO-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanenitrile Chemical compound FC(F)(F)C(F)(F)C#N MTLOQUGSPBVZEO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 239000007789 gas Substances 0.000 description 66
- 239000000047 product Substances 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 238000001514 detection method Methods 0.000 description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 17
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 239000007790 solid phase Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/263—Drying gases or vapours by absorption
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
- Y02P20/155—Perfluorocarbons [PFC]; Hydrofluorocarbons [HFC]; Hydrochlorofluorocarbons [HCFC]; Chlorofluorocarbons [CFC]
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to an adsorption purification recycling method for perfluoroisobutyronitrile/carbon dioxide recovered insulating gas, which comprises the following steps: (1) adsorption purification: introducing the recovered insulating gas into a fixed bed adsorption column filled with an adsorbent to remove most of organic impurities, water and HF; (2) gas reconstitution: and measuring the volume ratio of perfluoroisobutyronitrile/carbon dioxide in the adsorbed mixed gas, and directly recycling after the volume ratio is recombined. The adsorbent adopted by the invention can effectively adsorb impurities in the perfluoroisobutyronitrile recovered gas, wherein the adsorption rate of the organic impurities reaches 99.1%, and the adsorbent also has good removal effect on moisture and HF. The recovered insulating gas after one-time adsorption can meet the minimum requirement of impurities, the perfluoroisobutyronitrile and carbon dioxide are not required to be purified and blended respectively, and only the adsorbed gas is required to be supplemented to the required perfluoroisobutyronitrile/carbon dioxide ratio.
Description
Technical Field
The invention relates to a method for adsorbing, purifying and recycling gas, in particular to a method for adsorbing, purifying and recycling perfluoro-isobutyronitrile/carbon dioxide recovered insulating gas.
Background
The perfluoro-isobutyronitrile is a novel environment-friendly insulating gas and can be used for replacing sulfur hexafluoride in GIS, GIL and other electrical equipment. Perfluoroisobutyronitrile decomposes in electrical equipment due to discharge and overheat faults, producing corrosive decomposition products, some of which are highly toxic. There have been many reports on studies on products of electric discharge decomposition and thermal decomposition of perfluoroisobutyronitrile and a mixed gas thereof (a mixed insulating gas is generally obtained by using perfluoroisobutyronitrile and carbon dioxide in a molar ratio of 1:4).
Document "Decomposition properties of C 4 F 7 N/N 2 gas mixture:An environmentally friendly gas to replace SF 6 ，Industrial&Engineering Chemistry Research,2018,57,14,5173-5182 "C was studied by GC-MS 4 F 7 N/N 2 Is specified as C 2 F 6 、C 2 F 4 、CF 3 CN is the highest content of decomposition products. Literature "perfluoroisobutyronitrile under corona discharge (C) 4 F 7 N) and air mixture gas and its formation cause analysis, high voltage technology, volume 44, phase 10, 3174-3182 "implemented a series of industrial frequency AC corona discharge experiments, the results showed that perfluoro-isobutyronitrile (C) 4 F 7 N) and air mixed gas corona discharge decomposition products are mainly CO and CO 2 、CF 4 、C 2 F 6 、C 2 F 4 、C 3 F 6 、C 3 F 8 、C 4 F 8 、C 4 F 6 、CF 3 CN, etc. Literature "activated alumina and molecular sieve pair C 4 F 7 N/CO 2 And the adsorption properties of the overheat decomposition products thereof, the technical report of electrician, volume 35, phase 1, 88-96' explore the common adsorbents for C 4 F 7 N and its decomposition products, the experimental results show that: activated alumina can effectively adsorb C 2 F 3 N, but for C 4 F 7 N also has strong adsorption capacity and is not suitable for C 3 F 7 CN/CO 2 The mixed gas is used as an insulating medium in electric equipment.
In summary, the discharged or thermally decomposed perfluoroisobutyronitrile gas must be purified to remove toxic and harmful impurities before being recycled, and in addition, the recovery and reutilization are beneficial to further reducing the use cost due to the higher price of the perfluoroisobutyronitrile, which has important significance for popularization of the application of the perfluoroisobutyronitrile. Chinese patent "a method for separating mixed gas of heptafluoroisobutyronitrile and carbon dioxide" (CN 112979499A) is characterized by four steps: the patent application aims to separate the heptafluoroisobutyronitrile, the purified heptafluoroisobutyronitrile after four steps can be finally used in mixed gas, and the separation method is complex and wastes energy.
At present, no excessive reports are seen on the technical research on recycling of the perfluoroisobutyronitrile/carbon dioxide insulating gas recovered from the electrical equipment, so that a novel purification technology is necessary to be developed for purifying and recycling the perfluoroisobutyronitrile recovered gas, and the use requirement of the power industry is met.
Disclosure of Invention
The invention provides a simple and effective treatment method aiming at solving the problem of recycling after removing impurities in discharged or thermally decomposed perfluoro-isobutyronitrile/carbon dioxide recovered insulating gas, the method can efficiently adsorb and recover organic or inorganic impurities in the insulating gas, does not need to separate perfluoro-isobutyronitrile and carbon dioxide respectively, and only needs to supplement the adsorbed gas to the required ratio of perfluoro-isobutyronitrile/carbon dioxide.
An adsorption purification recycling method of perfluoroisobutyronitrile/carbon dioxide recovery insulating gas, wherein the perfluoroisobutyronitrile/carbon dioxide recovery insulating gas is perfluoroisobutyronitrile/carbon dioxide insulating gas subjected to discharge or thermal decomposition, and the method comprises the following steps: (1) adsorption purification: introducing the recovered insulating gas into a fixed bed adsorption column filled with an adsorbent to remove most of organic impurities, water and HF; (2) gas reconstitution: measuring the volume content ratio of perfluoroisobutyronitrile/carbon dioxide in the mixed gas obtained after adsorption, and directly recycling the mixed gas after the mixed gas is recombined to the volume ratio of perfluoroisobutyronitrile/carbon dioxide in the original insulating gas or the required insulating gas;
the adsorbent consists of an active component and a carrier, wherein the active component consists of one or more transition metal compounds and one or more alkali metal or/and alkaline earth metal compounds, the alkali metal is selected from Li, na, K, rb, cs, the alkaline earth metal is selected from Be, mg, ca, sr, ba, the transition metal is selected from Cu, ag, fe, co, ni, pd, pt, ta, la, ce, pr, nd, Y, sc, zn, the carrier is one or more of an X-type molecular sieve, a Y-type molecular sieve, an SBA-15-type molecular sieve and an HZSM-5-type molecular sieve, and the metal element load amount in the active component is 1.0% -25.0%.
The active components are loaded on the carrier, and the loading method is at least one of an ion exchange method, a mechanical mixing method and an impregnation method.
The ion exchange method is to mix and modify the carrier and the metal salt ion solution of the active component precursor, and obtain the modified adsorbent through drying at 80-150 ℃ and roasting at 200-400 ℃ after standing and cleaning; the concentration of the metal salt ion solution is 0.01-5mol/L, the solid-to-liquid ratio of the carrier to the metal salt ion solution is 1/1-1/50, and the metal salt ion exchange degree is 1.0% -99.9%;
the mechanical mixing method is to mix and bake the carrier and the metal salt of the active component precursor, wherein the mass ratio of the carrier to the metal salt is 1/0.1-1/5, and the baking temperature is 200-650 ℃;
the impregnation method is to mix and modify a carrier and a metal salt ion solution of an active component precursor, and obtain a modified adsorbent after standing and cleaning, drying at 80-150 ℃ and roasting at 200-400 ℃, wherein the concentration of the metal salt ion solution is 0.01-5mol/L, the solid-liquid ratio of the carrier and the metal salt ion solution is 1/1-1/20, the metal element load is 1.0-25.0%,
the metal salt is a mixture of one or more of chloride, nitrate or carbonate of transition metal and one or more of chloride, nitrate or carbonate of alkali metal or/and alkaline earth metal.
The total load of alkali metal or/and alkaline earth metal in the active component is 0.1-20%, the load of transition metal is 0.1-10%, and the active component precursor is nitrate or carbonate.
The alkali metal is Na and K, the alkaline earth metal is Mg and Ca, the transition metal is Cu, co, ni, pd, la, ce, zn, and the carrier is one or more of an X-type molecular sieve, an SBA-15-type molecular sieve and an HZSM-5-type molecular sieve.
The alkali metal is Na and K, the alkaline earth metal is Mg and Ca, the transition metal is Co, la, ce, zn, and the carrier is an X-type molecular sieve or an SBA-15 type molecular sieve.
The recovered insulating gas contains impurities of ethanedinitrile, trifluoroacetonitrile, pentafluoropropionitrile, hexafluoropropylene, HF, CO and H 2 O。
The volume ratio of perfluoroisobutyronitrile/carbon dioxide in the primary insulating gas is perfluoroisobutyronitrile/carbon dioxide=1: 4.
the adsorption purification reaction conditions of the step (1) are as follows: the adsorption temperature is 20-100 ℃, the adsorption pressure is 0-1MPa, and the feeding volume airspeed of the recovered insulating gas containing the perfluoro-isobutyronitrile is 1-1000h -1 。
The inner diameter of the adsorption column is 30mm, the length of the adsorption column is 600mm, the loading amount of the adsorbent is 200ml, and the product after adsorption is measured and quantitatively analyzed by a gas chromatograph.
The invention takes alkali metal or/and alkaline earth metal and transition metal as active components, and loads the active components on a specially selected carrier, and improves the carrier to obtain the adsorbent. The adsorbent has high adsorption rate to organic impurities, but has lower adsorption rate to heptafluoroisobutyronitrile, wherein the adsorption rate of the organic impurities reaches 99.1%, the adsorbent also has good removal effect to moisture and HF, the recovered insulating gas after primary adsorption can meet the minimum requirement of impurities, and the gas after adsorption can be directly recovered in the original workplace without purifying and re-preparing the perfluoroisobutyronitrile and the carbon dioxide respectively by adding the perfluoroisobutyronitrile and/or the carbon dioxide to the gas ratio of the original insulating gas or the gas ratio of the required insulating gas.
The beneficial effects are that:
1. the adsorbent used in the invention has excellent adsorption effect on the fluorine-containing nitrile impurities, and has good adsorption performance on moisture and acid gas; the minimum requirement of impurities can be met by one-time adsorption; the invention can directly recycle the adsorbed gas by supplementing the proportion of the full-fluorine isobutyronitrile or/and carbon dioxide to the original insulating gas without separating two main components respectively. The method is simple and practical, and greatly reduces the recycling cost.
2. The adsorbent used in the invention has the advantages of simple preparation process, good repeatability and low manufacturing cost; and the adsorbent has large adsorption capacity, long penetration time and good mechanical strength.
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples, which are not intended to limit the invention to these particular embodiments.
The impurity composition of the perfluoroisobutyronitrile recycle gas used in the examples of the present invention is shown in Table 1 below.
TABLE 1 composition of perfluoroisobutyronitrile recycle gas
The adsorbed product was quantitatively analyzed by GC-PDD: the adsorbed product was analyzed by GC-PDD helium ionization gas chromatograph, and various impurity contents in the product were quantitatively analyzed by single point external standard.
Chromatographic column: gaspro 30m 0.32 mm/CP-Molsive 5A 30m 0.53mm
Sample inlet temperature: 200 DEG C
Carrier gas flow rate: 2ml/min
Heating program: kept at 35 ℃ for 10min, and heated to 140 ℃ at a heating rate of 10 ℃/min for 15min.
The water content of the adsorbed product is detected by the method: reference to section 2 of determination of trace moisture in GB/T5832.2-2008 gas: dew point method, moisture detection.
The adsorbed product is subjected to a hydrogen fluoride content detection method: acidity detection is carried out by referring to GB/T34085-2017 gas trifluoromethane for electronic industry.
Example 1
Preparation of the adsorbent: weighing a certain amount of columnar active carbon particles (diameter 2-3 mm) as a carrier, and mixing with a metal salt solution according to a solid-to-liquid ratio of 1/3, wherein Cu (NO 3 ) 2 、KNO 3 、Ni(NO 3 ) 2 The concentration of (C) is 0.1mol/L, 0.08mol/L and 0.05mol/L respectively, and the mixture is kept stand and immersed for 8 hours at the room temperature of 25 ℃. Filtering, washing with deionized water until no Cu exists 2+ The detection is carried out, and the mixture is transferred into a baking oven at 120 ℃ for drying for 12 hours. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at the temperature of 250 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device with a loading amount of 200ml, and introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure) with a space velocity of 500h -1 The adsorbed product was quantitatively analyzed for impurity content by GC-PDD, and the results are shown in table 2. The adsorbed products were tested for moisture and hydrogen fluoride content and the results are shown in Table 4.
Example 2
Preparation of the adsorbent: weighing a certain amount of 10X molecular sieve (diameter of 3 mm) as carrier, mixing with metal salt solution at a solid-to-liquid ratio of 1/5, wherein Zn (NO 3 ) 2 、NaNO 3 、La(NO 3 ) 3 The concentration of (C) is 0.15mol/L, 0.1mol/L and 0.08mol/L respectively, and the mixture is kept stand and immersed for 8 hours at the temperature of 45 ℃. Filtering, washing with deionized water until no Zn exists 2+ And (3) detecting, and transferring the obtained product into a 150 ℃ oven for drying for 12 hours. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device with a loading amount of 200ml, and introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure) with a space velocity of 500h -1 The adsorbed product was quantitatively analyzed for impurity content by GC-PDD, and the results are shown in Table 2. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 4.
Example 3
Preparation of the adsorbent: weighing a certain amount of SBA-15 molecular sieve raw powder as a carrier, and mixing with a carbonate mixture of metal K, mg and Ce according to a mass ratio of 1/0.5, wherein K 2 CO 3 /MgCO 3 /Ce 2 (CO 3 ) 3 =1/0.5/0.5 (mass ratio). Adding a small amount of water as an adhesive, preparing a strip-shaped adsorbent with the diameter of 3mm by using a strip extruder, and transferring into a 120 ℃ oven for drying for 8 hours. Filling the dried adsorbent into a tubular electric furnace, introducing nitrogen, roasting for 12 hours at 350 ℃, and cooling to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device with a loading amount of 200ml, and introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure) with a space velocity of 500h -1 The adsorbed product was quantitatively analyzed for impurity content by GC-PDD, and the results are shown in Table 2. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 4.
Example 4
Preparation of the adsorbent: weighing a certain amount of 13X molecular sieve raw powder as a carrier, and mixing with a nitrate mixture of metals Ca, co and La according to a mass ratio of 1/1, wherein Ca (NO 3 ) 2 /Co(NO 3 ) 2 /La(NO 3 ) 3 =1/1/0.8 (mass ratio). Adding a small amount of dilute nitric acid with the concentration of 0.1mol/L as an adhesive, preparing a strip-shaped adsorbent with the diameter of 3mm by using a strip extruder, and transferring into a 120 ℃ oven for drying for 8 hours. Filling the dried adsorbent into a tubular electric furnace, introducing nitrogen, roasting for 12 hours at 350 ℃, and cooling to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device with a loading amount of 200ml, and introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure) with a space velocity of 500h -1 The adsorbed product was quantitatively analyzed for impurity content by GC-PDD, and the results are shown in Table 2. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 4.
Example 5
Preparation of the adsorbent: weighing a certain amount of spherical gamma-Al 2 O 3 (diameter 3 mm) as a carrier, and mixed with a metal salt solution in a solid-to-liquid ratio of 1/1.5, wherein KNO in the metal salt solution 3 、La(NO 3 ) 3 The concentration of (C) was 0.2mol/L and 0.12mol/L, respectively, and the mixture was stirred at room temperature at 65℃for 8 hours. Filtering, washing with deionized water until no K + The detection is carried out, and the mixture is transferred into a baking oven at 120 ℃ for drying for 12 hours. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device with a loading amount of 200ml, and introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure) with a space velocity of 500h -1 The adsorbed product was quantitatively analyzed for impurity content by GC-PDD, and the results are shown in Table 2. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 4.
Example 6
Preparation of the adsorbent: weighing a certain amount of spherical HZSM-5 (diameter of 3 mm) as a carrier, and mixing with a metal salt solution according to a solid-to-liquid ratio of 1/1.2, wherein PdCl in the metal salt solution 2 、Cu(NO 3 ) 2 The concentration of (C) was 0.1mol/L and 0.5mol/L, respectively, and the mixture was stirred at room temperature at 50℃for 8 hours. Filtering, washing with deionized water until no K + The detection is carried out, and the mixture is transferred into a baking oven at 120 ℃ for drying for 12 hours. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device with a loading amount of 200ml, and introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure) with a space velocity of 500h -1 The adsorbed product was quantitatively analyzed for impurity content by GC-PDD, and the results are shown in Table 2. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 4.
Example 7
Preparation of the adsorbent: a certain amount of activated carbon particles are weighed and dried in an oven at 120 ℃ for 12 hours. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 200 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device, filling 200ml, introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure), and quantitatively analyzing the impurity content of the adsorbed product by using GC-PDD, wherein the airspeed is 500h < -1 >, and the result is shown in Table 3. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 5.
Example 8
Preparation of the adsorbent: a certain amount of 10X molecular sieve (diameter 3 mm) was weighed and dried in an oven at 150 ℃ for 12h. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device, filling 200ml, introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure), and quantitatively analyzing the impurity content of the adsorbed product by using GC-PDD, wherein the airspeed is 500h < -1 >, and the result is shown in Table 3. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 5.
Example 9
Preparation of the adsorbent: a certain amount of SBA-15 molecular sieve (diameter 3 mm) was weighed and dried in an oven at 120℃for 8 hours. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device, filling 200ml, introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure), and quantitatively analyzing the impurity content of the adsorbed product by using GC-PDD, wherein the airspeed is 500h < -1 >, and the result is shown in Table 3. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 5.
Example 10
Preparation of the adsorbent: a certain amount of 13X molecular sieve (diameter 3 mm) was weighed and dried in an oven at 120 ℃ for 8h. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device, filling 200ml, introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure), and quantitatively analyzing the impurity content of the adsorbed product by using GC-PDD, wherein the airspeed is 500h < -1 >, and the result is shown in Table 3. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 5.
Example 11
Preparation of the adsorbent: weighing a certain amount of gamma-Al 2 O 3 Molecular sieves (3 mm diameter) were dried in an oven at 120℃for 12h. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device, filling 200ml, introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure), and quantitatively analyzing the impurity content of the adsorbed product by using GC-PDD, wherein the airspeed is 500h < -1 >, and the result is shown in Table 3. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 5.
Example 12
Preparation of the adsorbent: a certain amount of HZSM-5 molecular sieve (diameter 3 mm) was weighed and dried in an oven at 120 ℃ for 12h. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device, filling 200ml, introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure), and quantitatively analyzing the impurity content of the adsorbed product by using GC-PDD, wherein the airspeed is 500h < -1 >, and the result is shown in Table 3. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 5.
Example 13
Preparation of the adsorbent: weighing a certain amount of 10X molecular sieve raw powder as a carrier, and mixing with sodium carbonate according to a mass ratio of 1/0.5. Adding a small amount of water as an adhesive, preparing a strip-shaped adsorbent with the diameter of 3mm by using a strip extruder, and drying in an oven at 150 ℃ for 12 hours. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: will beLoading the treated adsorbent into a gas-solid phase adsorption device, charging 200ml, introducing perfluoroisobutyronitrile recycle gas at 25deg.C and 0.1MPa (absolute pressure), and air speed of 500h -1 The adsorbed product was quantitatively analyzed for impurity content by GC-PDD, and the results are shown in Table 3. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 5.
Example 14
Preparation of the adsorbent: weighing a certain amount of 13X molecular sieve raw powder as a carrier, and mixing with magnesium carbonate according to a mass ratio of 1/0.5. Adding a small amount of water as an adhesive, preparing a strip-shaped adsorbent with the diameter of 3mm by using a strip extruder, and drying in an oven at 120 ℃ for 8 hours. The dried adsorbent is filled in a tubular electric furnace, nitrogen is introduced into the tubular electric furnace for roasting for 12 hours at 350 ℃, and the adsorbent is cooled to room temperature for standby.
Application of the adsorbent: loading the treated adsorbent into a gas-solid phase adsorption device with a loading amount of 200ml, and introducing perfluoroisobutyronitrile recycle gas at 25 ℃ and 0.1MPa (absolute pressure) with a space velocity of 500h -1 The adsorbed product was quantitatively analyzed for impurity content by GC-PDD, and the results are shown in Table 3. The adsorbed product was subjected to moisture and hydrogen fluoride content detection, and the results are shown in Table 5.
TABLE 2 adsorption Effect of examples 1-6 on impurities in perfluoroisobutyronitrile
As can be seen from the data in Table 2, each example has obvious adsorption effect on most impurities in the perfluoroisobutyronitrile recovered gas, wherein the adsorption effect of examples 2-4 on various organic impurities is optimal, and particularly the total content of organic impurities is reduced from 2572.3ppm to 22.8ppm before and after the adsorption of example 4, the reduction amplitude reaches 99.1%, wherein the hexafluoropropylene content is only 2.2ppm, and the occupational contact limit value of all harmful factors in working fields is lower than part 2 of GBZ 2.1.1-2019: chemical harmful factorsHexafluoropropylene safety concentration 4mg/m 3 (equal to about 6.2 ppmv), but the adsorption effect on nitrogen and oxygen is not significant.
For a slightly higher impurity concentration, a secondary adsorption treatment may be performed.
TABLE 3 adsorption Effect of examples 7-14 on impurities in perfluoroisobutyronitrile
As can be seen from the data in Table 3, the adsorption of impurities in the recovered gas of perfluoroisobutyronitrile by the various adsorbents which were not modified was not remarkable, and the difference between the adsorbents added with transition metal was large in examples 8, 10 and 11, in which the adsorption of perfluoroisobutyronitrile was large, and the adsorbents modified with alkali metal or alkaline earth metal alone in examples 13 and 14 were not changed. In particular, examples 7 to 14 were extremely unsatisfactory in the adsorption effect of organic impurities.
TABLE 4 adsorption Effect of examples 1-6 on moisture and Hydrogen fluoride in perfluoroisobutyronitrile
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| H 2 O | 23.4ppmv | 7.8ppmv | 13.5ppmv | 6.4ppmv | 11.5ppmv | 15.3ppmv |
| HF | 0.1ppmv | <0.1ppmv | <0.1ppmv | <0.1ppmv | <0.1ppmv | <0.1ppmv |
As can be seen from the data in Table 4, each of the examples has significant adsorption of moisture and HF in the perfluoroisobutyronitrile recycle gas, wherein both the examples 2 and 4 can control the moisture content in the recycle gas to 10ppm or less, and each of the examples 1 to 6 can reduce the concentration of HF to 0.1ppm or less.
TABLE 5 adsorption Effect of examples 7-14 on moisture and Hydrogen fluoride in perfluoroisobutyronitrile
| Detecting items | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 |
| H 2 O | 26.4ppmv | 21.1ppmv | 19.4ppmv | 20.2ppm | 18.5ppmv | 19.3ppmv | 20.2ppmv | 19.8ppmv |
| HF | 0.2ppmv | 0.1ppmv | 0.1ppmv | <0.1ppmv | 0.1ppmv | 0.2ppm | <0.1ppmv | <0.1ppmv |
As can be seen from the data in Table 5, each adsorbent was specific to H 2 O and HF are bothThe water content of examples 9, 11, 12 and 14 was controlled to 20ppm or less, although the adsorption effect was not sufficient. Each example can reduce the HF concentration to below 0.2 ppm.
TABLE 6 perfluoroisobutyronitrile and CO in examples 7-14 2 Concentration contrast
| Detecting items | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 |
| CO 2 | 79.1％ | 81.9％ | 78.6％ | 83.3％ | 82.7％ | 79.2％ | 80.9％ | 82.9％ |
| Perfluoro-isobutyronitrile | 20.2％ | 17.5％ | 20.8％ | 16.1％ | 16.7％ | 20.2％ | 18.5％ | 16.5％ |
As can be seen from the data in Table 6, the examples are for perfluoroisobutyronitrile and CO 2 There was a degree of adsorption capacity, with examples 10, 11 and 14 having significant adsorption to perfluoroisobutyronitrile.
TABLE 7 perfluoroisobutyronitrile and CO in examples 1-6 2 Concentration contrast
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| CO 2 | 79.7％ | 78.3％ | 79.1％ | 75.4％ | 83.5％ | 78.6％ |
| Perfluoro-isobutyronitrile | 19.9％ | 21.4％ | 20.6％ | 24.3％ | 16.2％ | 21.1％ |
As can be seen from the data in Table 7, the examples are for perfluoroisobutyronitrile and CO 2 Having different adsorption capacities, example 4 for CO 2 Has obvious adsorption, the adsorption effect on the perfluoroisobutyronitrile is not obvious, while the adsorption effect on the perfluoroisobutyronitrile in the embodiment 5 is larger, and the perfluoroisobutyronitrile and CO in other embodiments 2 The concentration does not vary much.
From a comprehensive comparison, the examples 2-4 have better adsorption capacity on discharge decomposition products, have good deep removal effect on moisture and HF, and do not adsorb a large amount of perfluoroisobutyronitrile, thereby being beneficial to improving the recovery rate of perfluoroisobutyronitrile and reducing the recovery cost. In particular, the adsorption effect of example 4 was more excellent. CO can be supplemented to the mixed gas after the adsorption of the examples 2 to 4 2 The content was such that the perfluoroisobutyronitrile/carbon dioxide was restored to 1:4, directly using for recycling. And the perfluoroisobutyronitrile and carbon dioxide can be supplemented according to different working condition requirements, so that the perfluoroisobutyronitrile and carbon dioxide can be recovered to 1:4, or other ratios, such as 10:90.
Claims (10)
1. the adsorption purification recycling method of the perfluoroisobutyronitrile/carbon dioxide recovery insulating gas is characterized in that the perfluoroisobutyronitrile/carbon dioxide recovery insulating gas is discharged or thermally decomposed perfluoroisobutyronitrile/carbon dioxide insulating gas: the method comprises the following steps: (1) adsorption purification: introducing the recovered insulating gas into a fixed bed adsorption column filled with an adsorbent to remove most of organic impurities, water and HF; (2) gas reconstitution: measuring the volume content ratio of perfluoroisobutyronitrile/carbon dioxide in the mixed gas obtained after adsorption, and directly recycling the mixed gas after the mixed gas is recombined to the volume ratio of perfluoroisobutyronitrile/carbon dioxide in the original insulating gas or the required insulating gas;
the adsorbent consists of an active component and a carrier, wherein the active component consists of one or more transition metal compounds and one or more alkali metal or/and alkaline earth metal compounds, the alkali metal is selected from Li, na, K, rb, cs, the alkaline earth metal is selected from Be, mg, ca, sr, ba, the transition metal is selected from Cu, ag, fe, co, ni, pd, pt, ta, la, ce, pr, nd, Y, sc, zn, the carrier is one or more of an X-type molecular sieve, a Y-type molecular sieve, an SBA-15-type molecular sieve and an HZSM-5-type molecular sieve, and the metal element loading amount in the active component is 1.0-25.0%; the total loading of alkali metal or/and alkaline earth metal in the active component is 0.1-20%, and the loading of transition metal is 0.1-10%.
2. The method according to claim 1, characterized in that: the active components are loaded on the carrier, and the loading method is at least one of an ion exchange method, a mechanical mixing method and an impregnation method.
3. The method according to claim 2, characterized in that: the ion exchange method is to mix and modify the carrier and the metal salt ion solution of the active component precursor, and obtain the modified adsorbent through drying at 80-150 ℃ and roasting at 200-400 ℃ after standing and cleaning; the concentration of the metal salt ion solution is 0.01-5mol/L, the solid-to-liquid ratio of the carrier to the metal salt ion solution is 1/1-1/50, and the metal salt ion exchange degree is 1.0% -99.9%;
the mechanical mixing method is to mix and bake the carrier and the metal salt of the active component precursor, wherein the mass ratio of the carrier to the metal salt is 1/0.1-1/5, and the baking temperature is 200-650 ℃;
the impregnation method is to mix and modify a carrier and a metal salt ion solution of an active component precursor, and obtain a modified adsorbent after standing and cleaning, drying at 80-150 ℃ and roasting at 200-400 ℃, wherein the concentration of the metal salt ion solution is 0.01-5mol/L, the solid-liquid ratio of the carrier and the metal salt ion solution is 1/1-1/20, the metal element load is 1.0-25.0%,
the metal salt is a mixture of one or more of chloride, nitrate or carbonate of transition metal and one or more of chloride, nitrate or carbonate of alkali metal or/and alkaline earth metal.
4. The method according to claim 1, characterized in that: the active component precursor is nitrate and carbonate.
5. The method according to claim 4, wherein: the alkali metal is Na and K, the alkaline earth metal is Mg and Ca, the transition metal is Cu, co, ni, pd, la, ce, zn, and the carrier is one or more of an X-type molecular sieve, an SBA-15-type molecular sieve and an HZSM-5-type molecular sieve.
6. The method according to claim 5, wherein: the alkali metal is Na and K, the alkaline earth metal is Mg and Ca, the transition metal is Co, la, ce, zn, and the carrier is an X-type molecular sieve or an SBA-15 type molecular sieve.
7. The method according to claim 1, characterized in that: the recovered insulating gas contains impurities of ethanedinitrile, trifluoroacetonitrile, pentafluoropropionitrile, hexafluoropropylene, HF, CO and H 2 O。
8. The method according to claim 2, characterized in that: the volume ratio of perfluoroisobutyronitrile/carbon dioxide in the primary insulating gas is perfluoroisobutyronitrile/carbon dioxide=1: 4.
9. the method according to claim 1, characterized in that: the adsorption purification reaction conditions of the step (1) are as follows: the adsorption temperature is 20-100 ℃, the adsorption pressure is 0-1MPa, and the feeding volume airspeed of the perfluoroisobutyronitrile/carbon dioxide recovered insulating gas is 1-1000h -1 。
10. The method according to claim 2, characterized in that: the inner diameter of the adsorption column is 30mm, the length of the adsorption column is 600mm, the loading amount of the adsorbent is 200ml, and the mixed gas after adsorption is quantitatively analyzed by a gas chromatograph.
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