CN115340439A - Absorption purification method of hexafluorobutadiene - Google Patents
Absorption purification method of hexafluorobutadiene Download PDFInfo
- Publication number
- CN115340439A CN115340439A CN202110528608.1A CN202110528608A CN115340439A CN 115340439 A CN115340439 A CN 115340439A CN 202110528608 A CN202110528608 A CN 202110528608A CN 115340439 A CN115340439 A CN 115340439A
- Authority
- CN
- China
- Prior art keywords
- hexafluorobutadiene
- absorption
- liquid absorbent
- heptafluorobutene
- impurities
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 116
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000000746 purification Methods 0.000 title claims abstract description 53
- 239000002250 absorbent Substances 0.000 claims abstract description 99
- 230000002745 absorbent Effects 0.000 claims abstract description 99
- 239000012535 impurity Substances 0.000 claims abstract description 98
- 239000007788 liquid Substances 0.000 claims abstract description 98
- NUPBXTZOBYEVIR-UHFFFAOYSA-N 1,1,2,3,3,4,4-heptafluorobut-1-ene Chemical compound FC(F)C(F)(F)C(F)=C(F)F NUPBXTZOBYEVIR-UHFFFAOYSA-N 0.000 claims abstract description 96
- -1 amine compounds Chemical class 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- BLNWTWDBKNPDDJ-UHFFFAOYSA-N 1,1,1,2,3,4,4-heptafluorobut-2-ene Chemical compound FC(F)C(F)=C(F)C(F)(F)F BLNWTWDBKNPDDJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 5
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 5
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 5
- FYDLLXJLGCDGFH-UHFFFAOYSA-N 1,3,3,3-tetrafluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC=C(C(F)(F)F)C(F)(F)F FYDLLXJLGCDGFH-UHFFFAOYSA-N 0.000 claims abstract description 4
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004914 cyclooctane Substances 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940080818 propionamide Drugs 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229960002317 succinimide Drugs 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 26
- 239000012071 phase Substances 0.000 description 21
- 239000012043 crude product Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 238000012856 packing Methods 0.000 description 9
- 230000009471 action Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000895 extractive distillation Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WSJULBMCKQTTIG-OWOJBTEDSA-N (e)-1,1,1,2,3,4,4,4-octafluorobut-2-ene Chemical compound FC(F)(F)C(/F)=C(\F)C(F)(F)F WSJULBMCKQTTIG-OWOJBTEDSA-N 0.000 description 1
- ZVJOQYFQSQJDDX-UHFFFAOYSA-N 1,1,2,3,3,4,4,4-octafluorobut-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)F ZVJOQYFQSQJDDX-UHFFFAOYSA-N 0.000 description 1
- IRHYACQPDDXBCB-UHFFFAOYSA-N 1,2,3,4-tetrachloro-1,1,2,3,4,4-hexafluorobutane Chemical compound FC(F)(Cl)C(F)(Cl)C(F)(Cl)C(F)(F)Cl IRHYACQPDDXBCB-UHFFFAOYSA-N 0.000 description 1
- VEFCZMPFDXWPCP-UHFFFAOYSA-N 1-chloro-1,2,3,3,4,4,4-heptafluorobut-1-ene Chemical compound FC(Cl)=C(F)C(F)(F)C(F)(F)F VEFCZMPFDXWPCP-UHFFFAOYSA-N 0.000 description 1
- IEYGCJGIYKOOPE-UHFFFAOYSA-N 2-chloro-1,1,3,3,4,4,4-heptafluorobut-1-ene Chemical compound FC(F)=C(Cl)C(F)(F)C(F)(F)F IEYGCJGIYKOOPE-UHFFFAOYSA-N 0.000 description 1
- HUIOAUQSDRXHEQ-UHFFFAOYSA-M FC(F)=C(F)[Zn]Br Chemical compound FC(F)=C(F)[Zn]Br HUIOAUQSDRXHEQ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- WBCLXFIDEDJGCC-UHFFFAOYSA-N hexafluoro-2-butyne Chemical compound FC(F)(F)C#CC(F)(F)F WBCLXFIDEDJGCC-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D53/14—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 absorption
- B01D53/1487—Removing organic compounds
-
- 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
- B01D53/14—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 absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
- B01D53/14—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 absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
- B01D2252/2053—Other nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an absorption and purification method of hexafluorobutadiene, which comprises the following steps: in the presence of a liquid absorbent or an aqueous solution of the liquid absorbent, carrying out absorption purification on a composition containing hexafluorobutadiene and heptafluorobutene impurities; after absorption and purification, the removal rate of heptafluorobutene impurities is more than or equal to 95 percent; the liquid absorbent is at least one selected from cycloalkane, aromatic hydrocarbon, methyl chloride, organic amine compounds, amide compounds, nitrile compounds, five-membered or six-membered heterocyclic compounds, ester compounds and nitro compounds; the heptafluorobutene impurities comprise at least one of heptafluoromonochlorobutylene, heptafluoro-1-butene, heptafluoro-2-butene and heptafluoroisobutylene. The method has the advantages of high-efficiency removal of heptafluorobutene impurities, simple process, low energy consumption, high product purity, high yield, suitability for industrial application and the like.
Description
Technical Field
The invention relates to the field of fluorine chemical industry, in particular to a method for absorbing and purifying heptafluorobutene impurities in a crude product of hexafluorobutadiene by using a liquid absorbent.
Background
Hexafluorobutadiene, fully known as hexafluoro-1,3-butadiene, molecular formula CF 2 ＝CF-CF＝CF 2 The gas has a boiling point of 6 ℃ and a GWP of 290, and is widely used as a dry etching gas in the fields of semiconductors, integrated circuits, liquid crystals and the like. Compared with the traditional plasma etching gas, the etching selectivity of the hexafluorobutadiene is higher, and the hexafluorobutadiene is more suitable for the etching process with high aspect ratio. However, when hexafluorobutadiene is used as an etching gas, the requirement for the content of impurities is very strict, and the requirement must be strictly controlled to ppm (volume fraction) or even ppb level. Therefore, the purification technology of hexafluorobutadiene is of no great significance for its application in the field of electronics industry.
The development of a preparation process route of the hexafluorobutadiene mainly comprises two stages:
1) Early stage: mainly synthesizes 1,2,3,4-tetrachloro-1,1,2,3,4,4-hexafluorobutane by the processes of dimerization, fluorination and the like, and then zinc powder is dechlorinated in the presence of an alcohol solvent to obtain the catalyst. The preparation process has no heptafluorobutene impurity, needs high-risk gas (fluorine gas) in the reaction process, and needs to be operated at-70 ℃ under the ultralow temperature condition.
2) At the present stage: the self-coupling process of trifluorovinyl zinc bromide under the action of a metal oxidant has high reaction yield, low raw material cost and simple process, but the product of the process contains heptafluoro-1-butene, heptafluoro-2-butene, heptafluoroisobutylene, heptafluorochlorobutene and other impurities which can form azeotropy or near azeotropy with hexafluorobutadiene, and the impurities are difficult to remove, so that the process has certain challenge on obtaining high-purity products.
The US patent 6544319A discloses the use of a mean pore diameter of
The adsorbent of the method for adsorbing and purifying the hexafluobutadiene, but the method can cause the hexafluobutadiene to generate rearrangement reaction to generate hexafluoro-2-butyne when the adsorption is exothermic, the purity of the product is up to 99.99 percent, and the removal of heptafluorobutene impurities is not mentioned.
Chinese patent CN112169767A discloses a method for removing chlorocarbon impurities in hexafluorobutadiene by using an adsorbent, which has good adsorption selectivity and high adsorption capacity for chlorocarbon impurities, but is not suitable for removing heptafluorobutene impurities.
The Dajin patent CN111247120A discloses that crude products of hexafluorobutadiene containing octafluoro-1-butene, octafluoro-2-butene, heptafluoro-1-butene and heptafluoro-2-butene are distilled and purified by using oxygen-containing hydrocarbons such as alcohol, ketone and ether, halogenated saturated hydrocarbons, halogenated unsaturated hydrocarbons and the like as extraction solvents, and the hexafluorobutadiene with the highest purity of 99.99% is obtained in an extraction distillation tower with the theoretical plate number of 14. However, in the industrial application of the extractive distillation process, the energy consumption is high, the equipment structure is complex, the manufacturing cost is high, the temperature, the pressure and the like of an extractive distillation tower need to be strictly controlled during the extractive distillation purification, the requirement on automation control is high, and the total cost is higher.
Chinese Ship re-engineering patent CN109180424A discloses a method for removing organic solvent and carbon halogen in hexafluorobutadiene by sequentially adopting a first-stage rectifying tower, a second-stage rectifying tower, an adsorption tower and a third-stage rectifying towerSubstance, O 2 、N 2 、CO、CO 2 、H 2 Impurities such as O, particles and the like can reduce the cold and heat consumed in the purification process, but the whole process flow is longer, the yield is low, and the removal of heptafluorobutene impurities is not mentioned.
Therefore, aiming at heptafluorobutene impurities which are difficult to remove in a crude product of the hexafluorobutadiene, a hexafluorobutadiene purification method which is simple in process, low in energy consumption and suitable for industrial application is required, and the method has practical application value.
Disclosure of Invention
In order to solve the technical problems, the invention provides an absorption and purification method for heptafluorobutene impurities which are difficult to remove in a crude product of hexafluorobutadiene, and the method has the advantages of simple equipment, simple process, low energy consumption, easiness in automatic control, suitability for industrial production and the like.
The removal rate of the invention represents the content change of heptafluorobutene impurities in the composition before and after absorption and purification of the liquid absorbent, and the removal rate eta is calculated by the following method:
wherein, c 1 The content of heptafluorobutene impurities before absorption is expressed in ppm (volume fraction); c. C 2 The content of heptafluorobutene impurities after absorption is expressed in ppm (volume fraction).
The purpose of the invention is realized by the following technical scheme:
an absorption purification method of hexafluorobutadiene, said absorption purification method comprising:
in the presence of a liquid absorbent or an aqueous solution of the liquid absorbent, carrying out absorption purification on a composition containing hexafluorobutadiene and heptafluorobutene impurities; after absorption and purification, the removal rate of heptafluorobutene impurities is more than or equal to 95 percent;
the liquid absorbent is at least one selected from cycloalkane, aromatic hydrocarbon, methyl chloride, organic amine compounds, amide compounds, nitrile compounds, five-membered or six-membered heterocyclic compounds, ester compounds and nitro compounds;
the heptafluorobutene impurities comprise at least one of heptafluoromonochlorobutene, heptafluoro-1-butene, heptafluoro-2-butene and heptafluoroisobutylene.
Further, the cycloalkane is selected from at least one of cyclohexane, cycloheptane or cyclooctane;
the aromatic hydrocarbon is selected from at least one of benzene, toluene, styrene, phenol or cresol;
the chloromethane is at least one of dichloromethane, trichloromethane or carbon tetrachloride;
the organic amine compound is at least one of methylamine, aniline, ethylenediamine, diisopropylamine, triethanolamine or triethylamine;
the amide compound is at least one of formamide, acetamide, propionamide, caproamide, N-dimethylformamide, N-dimethylacetamide, benzamide or succinimide;
the nitrile compound is at least one of acetonitrile, propionitrile or butyronitrile;
the five-membered or six-membered heterocyclic compound is selected from at least one of pyridine, furan or 1,4-butyrolactone;
the ester compound is at least one of methyl formate, ethyl acetate or 3- (dimethylamino) ethyl acrylate;
the nitro compound is selected from nitromethane and/or nitroethane.
The absorption and purification method is realized by utilizing the solubility difference of the hexafluorobutadiene and the heptafluorobutene impurities in a specific liquid absorbent or an aqueous solution of the liquid absorbent, the larger the solubility difference is, the more favorable the removal of the heptafluorobutene impurities is, the more separation of the composition containing the hexafluorobutadiene and the heptafluorobutene impurities can be realized by the unit amount of the liquid absorbent, and the use amount of the liquid absorbent can be effectively reduced.
The phase equilibrium constant m can be compared with the solubility of the solute (component soluble in the liquid absorbent) in different liquid absorbents, and the smaller the value of the phase equilibrium constant m, the greater the solubility of the solute is. Since the liquid absorbent or the aqueous solution of the liquid absorbent is a dilute solution, close to an ideal solution, and the gas phase pressure of the system is also close to an ideal gas, a phase equilibrium constant m = y/x is obtained according to henry's law, where x is the liquid phase mole fraction of the solute in the liquid absorbent and y is the gas phase mole fraction of the poorly soluble component in the gas phase in equilibrium with the liquid phase, and both the liquid phase mole fraction and the gas phase mole fraction can be experimentally measured.
In the invention, in the presence of the liquid absorbent or the aqueous solution of the liquid absorbent, the phase equilibrium constant of the hexafluorobutadiene and heptafluorobutene impurities is in a closed interval of [0.1,0.9] or [1.2,4 ]. When the phase equilibrium constant is in the closed interval of [0.1,0.9], the liquid absorbent or the aqueous solution of the liquid absorbent has better solubility to heptafluorobutene impurities, and the hexafluorobutadiene is insoluble in the liquid absorbent or the aqueous solution of the liquid absorbent and is positioned in a gas phase; when the phase equilibrium constant is in the closed interval of [1.2,4], the liquid absorbent or the aqueous solution of the liquid absorbent has better solubility to hexafluorobutadiene, and the heptafluorobutene impurities are in the gas phase.
Preferably, the phase equilibrium constants of the hexafluorobutadiene and heptafluorobutene impurities are in the closed region of [0.25,0.55], the heptafluorobutene impurities are absorbed by the liquid absorbent or the aqueous solution of the liquid absorbent, and the hexafluorobutadiene is enriched in the gas phase.
In a preferred embodiment, the liquid absorbent is one or two selected from N, N-dimethylformamide, ethyl acetate and N, N-dimethylacetamide, and the removal rate of heptafluorobutene impurities is greater than or equal to 99% after absorption and purification. More preferably, the liquid absorbent is a mixed absorbent of N, N-dimethylformamide and ethyl acetate, and the mass ratio of the N, N-dimethylformamide to the ethyl acetate is (1-10): (10-0.1), preferably the mass ratio of the N, N-dimethylformamide to the ethyl acetate is (1-10): (1-2).
The amount of the liquid absorbent used in the present invention is not particularly limited, but considering that a very slight amount of dissolution of the liquid absorbent into the poorly soluble component is unavoidable, the mass ratio of the liquid absorbent to the composition is preferably (0.1 to 100): 1, more preferably (0.5 to 30): 1.
the absorption temperature and pressure are not particularly limited in the present invention. Generally, when the temperature is lowered and the total pressure is increased, the value of the phase equilibrium constant m is decreased, and the solubility of the difficultly separable component is increased, which is advantageous for the absorption operation. Therefore, it is preferable that the temperature for absorption and purification is 10 to 50 ℃ and the pressure is 0.001 to 1.0MPa.
The present invention is not particularly limited to the content of heptafluorobutene impurities in the composition containing hexafluorobutadiene and heptafluorobutene impurities. The content of the heptafluorobutene-based impurities in the composition is 1 to 10000ppm (volume fraction), preferably 10 to 3000ppm, in view of the absorption effect.
In order to further increase the yield of the absorption purification, the liquid absorbent or the aqueous solution of the liquid absorbent is subjected to a pretreatment step comprising: introducing the hexafluorobutadiene gas into a liquid absorbent or an aqueous solution of the liquid absorbent for pre-absorption.
The absorption purification method of the invention can be a static absorption method or a dynamic absorption method. The static absorption method comprises the steps of introducing a composition containing hexafluorobutadiene and heptafluorobutene impurities into a liquid absorbent or an aqueous solution of the liquid absorbent; the dynamic absorption method adopts a composition containing hexafluorobutadiene and heptafluorobutene impurities to reversely contact with a liquid absorbent or an aqueous solution of the liquid absorbent.
When a dynamic absorption method is adopted, the flow rate of the composition containing the hexafluorobutadiene and the heptafluorobutene impurities is 1-1000 g/min, and the flow rate of the liquid absorbent is 1-10000 g/min.
In practical production, the crude product of hexafluorobutadiene may include, in addition to heptafluorobutene impurities which are difficult to separate, for example, haloolefin, haloalkane, alkyne component and H 2 O、O 2 、N 2 、CO、CO 2 In order to remove part of possible impurities, the absorption purification method of the present invention further comprises:
the composition after absorption and purification is further subjected to at least one step of rectification, adsorption or membrane separation to obtain a hexafluorobutadiene product with the purity of more than or equal to 99.995%. More preferably, a hexafluorobutadiene product having a purity of not less than 99.999% is obtained.
The liquid absorbent or the aqueous solution of the liquid absorbent after absorption and purification of the invention can be subjected to regeneration treatment, and the regeneration treatment method comprises a gas purging method and/or a heating evaporation method, preferably a heating evaporation method. The regenerated liquid absorbent can be recycled.
In a preferred embodiment, the absorption purification method comprises an absorption purification step and an absorbent regeneration step, and specifically comprises the following steps:
(1) Absorption and purification: the composition containing the hexafluorobutadiene and the heptafluorobutene impurities enters an absorber to contact with a liquid absorbent or a water solution of the liquid absorbent to form a gas-liquid two-phase system, a component with lower solubility (such as the hexafluorobutadiene) is enriched in a gas phase, and a hexafluorobutadiene product with the heptafluorobutene impurity content of less than or equal to 1ppm (volume fraction) can be directly collected; the more soluble components (solute, such as heptafluorobutene impurities) remain in the liquid phase, forming the absorbent solution.
(2) Regeneration of an absorbent: the absorbent solution enters a regenerator, the absorbent without solute after regeneration returns to an absorber for recycling, and the solute-containing material flow flows out from the upper part of the regenerator.
The present invention also provides an absorption purification apparatus for hexafluorobutadiene, comprising:
the absorption tower is used for allowing a composition containing the hexafluorobutadiene and the heptafluorobutene impurities to enter the absorption tower from the lower part of the absorption tower and contact with a liquid absorbent or an aqueous solution of the liquid absorbent entering from the upper part of the absorption tower to form a gas-liquid two-phase, and the hexafluorobutadiene is enriched in a gas phase;
and the liquid absorbent after absorption enters the regenerator from the lower part of the absorption tower, and the liquid absorbent after regeneration returns to the absorption tower.
The absorption tower is a packed tower or a plate tower.
Compared with the prior art, the invention has the beneficial effects that:
according to the absorption and purification method of the hexafluorobutadiene, the adopted liquid absorbent has larger solubility difference between the hexafluorobutadiene and heptafluorobutene impurities, the content of the heptafluorobutene impurities which are difficult to remove is controlled within 1ppm (volume fraction), and the hexafluorobutadiene product with high purity and high yield can be obtained by using a simple process, simple operation and low energy consumption, so that the method is suitable for industrial application.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
In the embodiment of the invention, the liquid absorbent is adopted to absorb and purify the composition containing the hexafluorobutadiene and the heptafluorobutene impurities, and the composition can also directly adopt a crude product of the hexafluorobutadiene containing the heptafluorobutene impurities.
Different liquid absorbents are adopted to absorb the composition containing the hexafluorobutadiene and the heptafluorobutene impurities, the mole fractions before and after absorption are measured, and the phase equilibrium constant m of the hexafluorobutadiene and the heptafluorobutene impurities is calculated and obtained, and the results are shown in the following table 1:
TABLE 1 phase equilibrium constants of heptafluorobutene impurities in hexafluorobutadiene with different liquid absorbents
Example 1
In this embodiment, the absorption and purification of a crude product of hexafluorobutadiene with a heptafluorobutene impurity content of 6000ppm (volume fraction) specifically includes the following steps:
controlling the temperature of an absorption tower (a packed tower, wherein the packing is phi 3 multiplied by 3mm Dike pine packing, and the height of the packing is 4 m) to be 20 ℃ and the pressure to be 0.02MPa;
the crude product of the hexafluorobutadiene enters the absorption tower from the lower part of the absorption tower in a gas form, and the flow rate is 10g/min; the ethyl acetate as the absorbent enters the absorption tower from the upper part of the absorption tower in a liquid state, the flow rate is 60g/min, namely the mass ratio of the ethyl acetate to the crude product of the hexafluorobutadiene is 6:1;
the crude gas of the hexafluorobutadiene is in reverse contact with the ethyl acetate liquid in the absorption tower, mass transfer is sufficient, the ethyl acetate solution in which the heptafluorobutene impurities are dissolved is gathered at the lower part of the absorption tower under the action of gravity, and the hexafluorobutadiene from which the heptafluorobutene impurities are removed is gathered at the upper part of the absorption tower.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 28ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 99.53%.
Example 2
The operation of this example is the same as example 1 except that: n, N-Dimethylformamide (DMF) was used as a liquid absorbent.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 7ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 99.88%.
Example 3
In this embodiment, the absorption and purification of the crude hexafluorobutadiene product with heptafluorobutene impurity content of 500ppm (volume fraction) specifically includes the following steps:
controlling the temperature of an absorption tower (a packed tower, wherein the packing is phi 3 multiplied by 3mm Dike pine packing, and the height of the packing is 4 m) to be 15 ℃ and the pressure to be 0.05MPa;
the crude product of the hexafluorobutadiene enters the absorption tower from the lower part of the absorption tower in a gas form, and the flow rate is 10g/min; the DMF enters the absorption tower from the upper part of the absorption tower in a liquid state, the flow rate is 40g/min, namely the mass ratio of the DMF to the crude hexafluorobutadiene product is 4:1;
the crude product gas of the hexafluorobutadiene is in reverse contact with DMF liquid in an absorption tower, mass transfer is fully carried out, DMF solution in which heptafluorobutene impurities are dissolved is gathered at the lower part of the absorption tower under the action of gravity, and the hexafluorobutadiene from which the heptafluorobutene impurities are removed is enriched at the upper part of the absorption tower.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 2ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 99.60%.
Example 4
In this example, the absorption and purification of a crude hexafluorobutadiene product containing heptafluorobutene impurities in an amount of 2000ppm (volume fraction) specifically includes the following steps:
controlling the temperature of an absorption tower (a packed tower, wherein the packing is phi 3 multiplied by 3mm Dike pine packing, and the height of the packing is 4 m) to be 20 ℃ and the pressure to be 0.05MPa;
the crude product of the hexafluorobutadiene enters the absorption tower from the lower part of the absorption tower in a gas form, and the flow rate is 8g/min; the DMF enters the absorption tower from the upper part of the absorption tower in a liquid state, the flow rate is 80g/min, namely the mass ratio of the DMF to the crude hexafluorobutadiene product is 10;
the crude product gas of the hexafluorobutadiene is in reverse contact with DMF liquid in an absorption tower, mass transfer is fully carried out, DMF solution in which heptafluorobutene impurities are dissolved is gathered at the lower part of the absorption tower under the action of gravity, and the hexafluorobutadiene from which the heptafluorobutene impurities are removed is enriched at the upper part of the absorption tower.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 1ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 99.95%.
Example 5
The operation of this example is the same as example 4, except that: using N, N-dimethylformamide: the mixed solution of ethyl acetate =6:1 (mass ratio) is used as a liquid absorbent, the mass ratio of the liquid absorbent to the crude product of the hexafluorobutadiene is controlled to be 6:1 (for example, the flow rate of the liquid absorbent is 60g/min, the flow rate of the pure product of the hexafluorobutadiene is 10 g/min), the pressure of the absorption tower is 0.1MPa, and the rest is unchanged.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 1ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 99.95%.
Example 6
The operation of this example is the same as example 4, except that: the mass ratio of DMF to the crude hexafluorobutadiene was controlled to 6:1 (the flow rate of DMF was reduced to 48 g/min), and the rest was unchanged.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 1ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 99.95%. Compared with example 4, it can be seen that, to a certain extent, the mass ratio of the liquid absorbent to the crude hexafluorobutadiene product is continuously increased, so that the removal rate of the heptafluorobutene impurities is not continuously increased.
Hexafluorobutadiene enriched in the upper part of the absorption column and freed from heptafluorobutene impurities was collected continuously and 419g was collected in 60 minutes, i.e., the yield of hexafluorobutadiene was 87.29%.
Example 7
The operation of this example is the same as example 6, except that: pre-treating DMF as a liquid absorbent, the pre-treating step comprising: introducing high-purity hexafluorobutadiene gas into a DMF solution, wherein the flow rate is 5g/min, the duration is 60 minutes, the DMF solution absorbing trace hexafluorobutadiene is used as a liquid absorbent, and the rest operations are unchanged.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 1ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 99.95%.
Hexafluorobutadiene enriched in the upper part of the absorption column and freed from heptafluorobutene impurities was collected continuously for 60 minutes in 471g, i.e. the yield of hexafluorobutadiene was 98.13%.
Example 8
The operation of this example is the same as example 4, except that: acetonitrile is used as a liquid absorbent. The flow rate of the crude product of the hexafluorobutadiene is 10g/min; the flow rate of the acetonitrile is 40g/min, namely the mass ratio of the acetonitrile to the crude product of the hexafluorobutadiene is 4:1;
detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 34ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 98.30%.
Example 9
The operation of this example is the same as example 8, except that: pyridine is used as the liquid absorbent.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 45ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 97.75%.
Example 10
The operation of this example is the same as example 8, except that: benzene was used as the liquid absorbent.
Detection and analysis show that the content of the heptafluorobutene impurities in the hexafluorobutadiene after absorption and purification is 36ppm (volume fraction), and the removal rate of the heptafluorobutene impurities is 98.20%.
Example 11
In this example, the DMF solution containing heptafluorobutene impurities dissolved therein, which had been collected in the lower part of the absorption column in example 7, was fed into a regenerator at a flow rate of 48g/min and was regenerated by heating evaporation at a regeneration temperature of 120 ℃ under a pressure of 0.03MPa.
The regenerated DMF solution is returned to the absorption tower and is used as an absorbent together with fresh liquid absorbent. The regeneration recovery rate of the absorbent reaches 98 percent through calculation.
After the liquid absorbent undergoes 6 times of absorption and 6 times of regeneration cycles, the removal rate of the heptafluorobutene impurities is not obviously reduced and is still maintained at about 99.9 percent.
Example 12
In the crude hexafluorobutadiene product of this example, besides heptafluorobutene impurities, trifluoroethylene, chlorotrifluoroethylene, trifluorobromoethylene, and H are also included 2 O、O 2 、N 2 、CO、CO 2 And the like.
In this example, in addition to the operation of example 4, the heptafluorobutene impurity-removed hexafluorobutadiene enriched in the upper part of the absorption column was fed to a rectification column and rectified to remove trifluoroethylene, chlorotrifluoroethylene, trifluorobromoethylene, and H 2 O、O 2 、N 2 、CO、CO 2 And the impurities are mixed, and high-purity hexafluorobutadiene gas with the purity of 99.999 percent (volume fraction) is obtained at the top of the rectifying tower.
Claims (15)
1. A method for absorbing and purifying hexafluorobutadiene is characterized in that: the absorption purification method comprises the following steps:
in the presence of a liquid absorbent or an aqueous solution of the liquid absorbent, carrying out absorption purification on a composition containing hexafluorobutadiene and heptafluorobutene impurities; after absorption and purification, the removal rate of heptafluorobutene impurities is more than or equal to 95 percent;
the liquid absorbent is at least one selected from cycloalkane, aromatic hydrocarbon, methyl chloride, organic amine compounds, amide compounds, nitrile compounds, five-membered or six-membered heterocyclic compounds, ester compounds and nitro compounds;
the heptafluorobutene impurities comprise at least one of heptafluoromonochlorobutylene, heptafluoro-1-butene, heptafluoro-2-butene and heptafluoroisobutylene.
2. The method for absorbing and purifying hexafluorobutadiene as claimed in claim 1, wherein:
the cycloalkane is selected from at least one of cyclohexane, cycloheptane or cyclooctane;
the aromatic hydrocarbon is selected from at least one of benzene, toluene, styrene, phenol or cresol;
the chloromethane is at least one of dichloromethane, trichloromethane or carbon tetrachloride;
the organic amine compound is selected from at least one of methylamine, aniline, ethylenediamine, diisopropylamine, triethanolamine or triethylamine;
the amide compound is selected from at least one of formamide, acetamide, propionamide, caproamide, N-dimethylformamide, N-dimethylacetamide, benzamide or succinimide;
the nitrile compound is at least one of acetonitrile, propionitrile or butyronitrile;
the five-membered or six-membered heterocyclic compound is selected from at least one of pyridine, furan or 1,4-butyrolactone;
the ester compound is at least one of methyl formate, ethyl acetate or 3- (dimethylamino) ethyl acrylate;
the nitro compound is selected from nitromethane and/or nitroethane.
3. The method for absorbing and purifying hexafluorobutadiene as claimed in claim 2, wherein: in the presence of the liquid absorbent or the aqueous solution of the liquid absorbent, the phase equilibrium constant of the hexafluorobutadiene and heptafluorobutene impurities is in a closed interval of [0.1,0.9] or [1.2,4 ].
4. The method for absorbing and purifying hexafluorobutadiene as claimed in claim 3, wherein: in the presence of the liquid absorbent or the aqueous solution of the liquid absorbent, the phase equilibrium constant of the hexafluorobutadiene and heptafluorobutene impurities is in a closed interval of [0.25,0.55 ].
5. The method for absorbing and purifying hexafluorobutadiene as claimed in claim 1, wherein: the liquid absorbent is one or two of N, N-dimethylformamide, ethyl acetate and N, N-dimethylacetamide, and the removal rate of heptafluorobutene impurities is more than or equal to 99% after absorption and purification.
6. The method for absorbing and purifying hexafluorobutadiene as claimed in claim 5, wherein: the liquid absorbent is a mixed absorbent of N, N-dimethylformamide and ethyl acetate, and the mass ratio of the N, N-dimethylformamide to the ethyl acetate is (1-10): (10-0.1).
7. The method for absorbing and purifying hexafluorobutadiene as claimed in claim 1, wherein: the mass ratio of the liquid absorbent to the composition is (0.1-100): 1.
8. the method for absorbing and purifying hexafluorobutadiene as claimed in claim 1, wherein: the liquid absorbent or aqueous solution of liquid absorbent is subjected to a pre-treatment step comprising: introducing the hexafluorobutadiene gas into a liquid absorbent or an aqueous solution of the liquid absorbent for pre-absorption.
9. The method for absorbing and purifying hexafluorobutadiene as claimed in claim 1, wherein: the absorption purification method comprises a static absorption method and a dynamic absorption method, wherein the static absorption method adopts the step of introducing a composition containing hexafluorobutadiene and heptafluorobutene impurities into a liquid absorbent or an aqueous solution of the liquid absorbent; the dynamic absorption method adopts a composition containing hexafluorobutadiene and heptafluorobutene impurities to reversely contact with a liquid absorbent or an aqueous solution of the liquid absorbent.
10. The absorption purification method of hexafluorobutadiene as claimed in claim 9, wherein: when a dynamic absorption method is adopted, the flow rate of the composition containing the hexafluorobutadiene and the heptafluorobutene impurities is 1-1000 g/min, and the flow rate of the liquid absorbent is 1-10000 g/min.
11. The absorption purification method of hexafluorobutadiene as claimed in any one of claims 1 to 10, characterized in that: the absorption and purification temperature is 10-50 ℃, and the pressure is 0.001-1.0 MPa.
12. The method for absorbing and purifying hexafluorobutadiene as claimed in claim 1, wherein: the content of heptafluorobutene impurities in the composition is 1-10000 ppm.
13. The absorption purification method of hexafluorobutadiene as claimed in claim 12, wherein: the composition after absorption and purification is further subjected to at least one step of rectification, adsorption or membrane separation to obtain a hexafluorobutadiene product with the purity of more than or equal to 99.995%.
14. An absorption purification device of hexafluorobutadiene is characterized in that: the absorption purification apparatus includes:
the absorption tower is used for allowing a composition containing the hexafluorobutadiene and the heptafluorobutene impurities to enter the absorption tower from the lower part of the absorption tower and contact with a liquid absorbent or an aqueous solution of the liquid absorbent entering from the upper part of the absorption tower to form a gas-liquid two-phase, and the hexafluorobutadiene is enriched in a gas phase;
and the liquid absorbent after absorption enters the regenerator from the lower part of the absorption tower, and the liquid absorbent after regeneration returns to the absorption tower.
15. The apparatus for absorbing and purifying hexafluorobutadiene as claimed in claim 14, wherein: the absorption tower is a packed tower or a plate tower.
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| CN111247120A (en) * | 2017-10-23 | 2020-06-05 | 大金工业株式会社 | Process for producing hexafluorobutadiene |
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| GB793025A (en) * | 1955-05-09 | 1958-04-09 | Bofors Ab | Apparatus for the continuous mixing and separation of two immiscible liquids of different specific gravities |
| US6544319B1 (en) * | 2002-01-16 | 2003-04-08 | Air Products And Chemicals, Inc. | Purification of hexafluoro-1,3-butadiene |
| CN105712820A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Novel technology for concentrating post-MTBE C4 |
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