CA2104654A1 - Process for the preparation of fluorinated ethanic compounds - Google Patents
Process for the preparation of fluorinated ethanic compoundsInfo
- Publication number
- CA2104654A1 CA2104654A1 CA002104654A CA2104654A CA2104654A1 CA 2104654 A1 CA2104654 A1 CA 2104654A1 CA 002104654 A CA002104654 A CA 002104654A CA 2104654 A CA2104654 A CA 2104654A CA 2104654 A1 CA2104654 A1 CA 2104654A1
- Authority
- CA
- Canada
- Prior art keywords
- uranium hexafluoride
- compound
- ethylene
- uranium
- fluorinated
- 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.)
- Abandoned
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 29
- 238000002360 preparation method Methods 0.000 title description 3
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 2
- 238000003682 fluorination reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 5
- 229910052770 Uranium Inorganic materials 0.000 description 4
- VUWZPRWSIVNGKG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH2] VUWZPRWSIVNGKG-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 4
- BQNSLJQRJAJITR-UHFFFAOYSA-N 1,1,2-trichloro-1,2-difluoroethane Chemical compound FC(Cl)C(F)(Cl)Cl BQNSLJQRJAJITR-UHFFFAOYSA-N 0.000 description 3
- -1 HCFC-122a compound Chemical class 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 235000019000 fluorine Nutrition 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MZFRHHGRNOIMLW-UHFFFAOYSA-J uranium(4+);tetrafluoride Chemical compound F[U](F)(F)F MZFRHHGRNOIMLW-UHFFFAOYSA-J 0.000 description 3
- RDTZCQIUXDONLZ-UHFFFAOYSA-N 1,1,1-trichloro-2,2-difluoroethane Chemical compound FC(F)C(Cl)(Cl)Cl RDTZCQIUXDONLZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- 229940051271 1,1-difluoroethane Drugs 0.000 description 1
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 description 1
- IDSKMUOSMAUASS-UHFFFAOYSA-N 1,2-dichloro-1,2-difluoroethane Chemical compound FC(Cl)C(F)Cl IDSKMUOSMAUASS-UHFFFAOYSA-N 0.000 description 1
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 1
- UOVSDUIHNGNMBZ-UHFFFAOYSA-N 1-chloro-1,2-difluoroethane Chemical compound FCC(F)Cl UOVSDUIHNGNMBZ-UHFFFAOYSA-N 0.000 description 1
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G43/00—Compounds of uranium
- C01G43/04—Halides of uranium
- C01G43/06—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Abstract The present invention provides a process for preparing an fluorinated ethanic organic compound, which comprises:
reacting ethylene or a halogenated ethylenic compound with uranium hexafluoride at a high temperature wherein the molar ratio of ethylene or the halogenated ethylenic compound to uranium hexafluoride ranges from 1:1 to 1.2:1.
reacting ethylene or a halogenated ethylenic compound with uranium hexafluoride at a high temperature wherein the molar ratio of ethylene or the halogenated ethylenic compound to uranium hexafluoride ranges from 1:1 to 1.2:1.
Description
:` ` "
PROCESS FOR THE PREPARATION OF FLVORINATED
. ETHANIC COMPOUNDS
. .
~ Field of the Invention .
The present invention relates to a process for preparing . halogenated organic compounds; and, particularly to a process ;' for preparing fluorinated ethanic compounds as a substitute for CFC(chlorofluorocarbon) known to be destructive of the ozone layer.
Backaround of the Invention ... .
There are a number of catalytic methods known for the manufacture of fluorinated ethanic compounds. In the Proposal ; on Replacement of the Freons Destroying the Earth's Ozone Layer with Ozone-Safe substitutes(Proceedings of All-Vnion Conference on Refrigerating and Ozone-Safe Freons, Leningrad, Ozone-Safe, 1989), there is provided a catalytic . ..~
. 20 hydrofluorination for the preparation of fluorinated ethanic .compounds, which uses antimony pentachloride as a catalyst in liquid phase. The process is carried out at a temperature ;. ranging from 130 to 160C and a pressure ranging from 6 to 8 . kg/cm2G. The hydrofluorination in gaseous phase is carried 25 out at a temperature ranging from 150 to 350C on a catalyst.
. ., ~ The prior methods for manufacturing a chlorofluorocarbon ., .
., .
~ .
., ~ .
:;~ ' ' : : .
.
5 ~
.. .
PROCESS FOR THE PREPARATION OF FLVORINATED
. ETHANIC COMPOUNDS
. .
~ Field of the Invention .
The present invention relates to a process for preparing . halogenated organic compounds; and, particularly to a process ;' for preparing fluorinated ethanic compounds as a substitute for CFC(chlorofluorocarbon) known to be destructive of the ozone layer.
Backaround of the Invention ... .
There are a number of catalytic methods known for the manufacture of fluorinated ethanic compounds. In the Proposal ; on Replacement of the Freons Destroying the Earth's Ozone Layer with Ozone-Safe substitutes(Proceedings of All-Vnion Conference on Refrigerating and Ozone-Safe Freons, Leningrad, Ozone-Safe, 1989), there is provided a catalytic . ..~
. 20 hydrofluorination for the preparation of fluorinated ethanic .compounds, which uses antimony pentachloride as a catalyst in liquid phase. The process is carried out at a temperature ;. ranging from 130 to 160C and a pressure ranging from 6 to 8 . kg/cm2G. The hydrofluorination in gaseous phase is carried 25 out at a temperature ranging from 150 to 350C on a catalyst.
. ., ~ The prior methods for manufacturing a chlorofluorocarbon ., .
., .
~ .
., ~ .
:;~ ' ' : : .
.
5 ~
.. .
are generally based on the concept of replacing the chlorine atoms with fluorine atoms.
For example, United States Patent No. 3,235,608(1966) describes the fluorination process of chlorinated or fluoro-chlorinated C1_12 hydrocarbons using uranium hexafluoride. Thefluorination is conducted by employing an inorganic fluoride - catalyst such as fluorides of sodium, potassium, calcium, etc.
in a fluidized bed at a temperature ranging from 70 to 600C.
However, this method is not economical since it requires the fluoride catalyst and an excess amount of uranium ; hexafluoride.
Further, United States Patent No. 3,382,049 describes a . method of fluorinating trichloroethylene by employing uranium hexafluoride. The main purpose of fluorination in this method . 15 is to obtain uranium tetrafluoride, and, therefore, detailed i information on organic compound, an auxiliary product, is not provided. Furthermore, it is observed that any excess amount : of uranium hexafluoride in the reactor may destroy the HCFC-122a compound produced to CFC-113 compound.
The present inventors have pursued to solve the . ., above-mentioned problems; and, as a result, succeeded in developing a method for preparing a fluorinated ethanic compound, which can be less harmful to the ozone layer, by lowering the excess amount of ethylenic compound as starting .. 25 material to uranium hexafluoride as a catalyst a during the .~i reaction between said two components.
:, .
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. .
..:'.
.
~: . ' . . :
` " ~lU'1~4 Summarv of the Invention ., . Accordingly, it is an object of the present invention to ~ provide an improved process for preparing a fluorinated ethanic compound.
. In accordance with one aspect of the invention, there is . provided a process for preparing a fluorinated ethanic : compound, which comprises reacting ethylene or a halogenated ethylenic compound with uranium hexafluoride at an elevated temperature wherein the molar ratio of ethylene or the halogenated ethylenic compound to uranium hexafluoride ranges from 1:1 to 1.2:1.
~,.
.,; .
:S;: Detailed Description of the Invention .:: In the process of the present invention, a fluorinated i. organic compound is obtained by the fluorination of an ::: unsaturated ethylenic compound with uranium hexafluoride as . ~.
shown in the following reaction formula(1):
:: 20 ~ C = C~ + UF6 - ,CF - CF~ + ~F4 (1) .
;.................. The halogenated ethylenic compo~lnd used ln the process of :.
the present invention may lnclude trichloroethylene(C2HCl3), . 25 vinylidene chlorlde(C2H2Cl2), vinylchloride(C2H3Cl), vinylidene -fluoride(C2H2F2) and the like.
.':1~.
, ' ' ' ~''.' ' The uranium hexafluoride may be diluted with an inert diluent gas to make a concentration of 20-100% by volume for the fluorination reaction, particularly for obtaining a stable organic compound. The inert diluent may include nitrogen, neon, argon and the like. As a diluent, the product, fluorine-containing orgainc substances may be employed by recycling.
The choice of the limited molar ratios pertaining to ethylene or the halogerJated ethylenic compound and uranium hexafluoride to be fed is based on the fact that if uranium hexafluoride is fed in an amount greater than the upper limit , of the range, it makes the end product to be subjected to degradation or decomposi-tion due to its interreaction with the excessive uranium hexafluoride; and, if uranium hexafluoride is fed in a smaller amount than the lower limit, it leads to an overexpenditure of ethylene or the halogenated ethylenic ., compound and overall impairment of the final product.
. Ethylene or the halogenated ethylenic compound is preferably fed into the reactor in a dispersed form, thereby to improve the reaction efficiency and to provide the desirable fluorination process in the flare. Accordingly, the reaction of ethylene or the halogenated ethylenic compound with uranium hexafluoride is carried out by spraying each component into the reaction system and mixing and contacting with each other.
,~, The fluorination reactlon ls conducted at an elevated temperature ranglng from 80 to 400C, preferably 100 to 350C
. .. . ..
.:
:
:. : .
... , , .
. .:
For example, United States Patent No. 3,235,608(1966) describes the fluorination process of chlorinated or fluoro-chlorinated C1_12 hydrocarbons using uranium hexafluoride. Thefluorination is conducted by employing an inorganic fluoride - catalyst such as fluorides of sodium, potassium, calcium, etc.
in a fluidized bed at a temperature ranging from 70 to 600C.
However, this method is not economical since it requires the fluoride catalyst and an excess amount of uranium ; hexafluoride.
Further, United States Patent No. 3,382,049 describes a . method of fluorinating trichloroethylene by employing uranium hexafluoride. The main purpose of fluorination in this method . 15 is to obtain uranium tetrafluoride, and, therefore, detailed i information on organic compound, an auxiliary product, is not provided. Furthermore, it is observed that any excess amount : of uranium hexafluoride in the reactor may destroy the HCFC-122a compound produced to CFC-113 compound.
The present inventors have pursued to solve the . ., above-mentioned problems; and, as a result, succeeded in developing a method for preparing a fluorinated ethanic compound, which can be less harmful to the ozone layer, by lowering the excess amount of ethylenic compound as starting .. 25 material to uranium hexafluoride as a catalyst a during the .~i reaction between said two components.
:, .
.
.
. .
..:'.
.
~: . ' . . :
` " ~lU'1~4 Summarv of the Invention ., . Accordingly, it is an object of the present invention to ~ provide an improved process for preparing a fluorinated ethanic compound.
. In accordance with one aspect of the invention, there is . provided a process for preparing a fluorinated ethanic : compound, which comprises reacting ethylene or a halogenated ethylenic compound with uranium hexafluoride at an elevated temperature wherein the molar ratio of ethylene or the halogenated ethylenic compound to uranium hexafluoride ranges from 1:1 to 1.2:1.
~,.
.,; .
:S;: Detailed Description of the Invention .:: In the process of the present invention, a fluorinated i. organic compound is obtained by the fluorination of an ::: unsaturated ethylenic compound with uranium hexafluoride as . ~.
shown in the following reaction formula(1):
:: 20 ~ C = C~ + UF6 - ,CF - CF~ + ~F4 (1) .
;.................. The halogenated ethylenic compo~lnd used ln the process of :.
the present invention may lnclude trichloroethylene(C2HCl3), . 25 vinylidene chlorlde(C2H2Cl2), vinylchloride(C2H3Cl), vinylidene -fluoride(C2H2F2) and the like.
.':1~.
, ' ' ' ~''.' ' The uranium hexafluoride may be diluted with an inert diluent gas to make a concentration of 20-100% by volume for the fluorination reaction, particularly for obtaining a stable organic compound. The inert diluent may include nitrogen, neon, argon and the like. As a diluent, the product, fluorine-containing orgainc substances may be employed by recycling.
The choice of the limited molar ratios pertaining to ethylene or the halogerJated ethylenic compound and uranium hexafluoride to be fed is based on the fact that if uranium hexafluoride is fed in an amount greater than the upper limit , of the range, it makes the end product to be subjected to degradation or decomposi-tion due to its interreaction with the excessive uranium hexafluoride; and, if uranium hexafluoride is fed in a smaller amount than the lower limit, it leads to an overexpenditure of ethylene or the halogenated ethylenic ., compound and overall impairment of the final product.
. Ethylene or the halogenated ethylenic compound is preferably fed into the reactor in a dispersed form, thereby to improve the reaction efficiency and to provide the desirable fluorination process in the flare. Accordingly, the reaction of ethylene or the halogenated ethylenic compound with uranium hexafluoride is carried out by spraying each component into the reaction system and mixing and contacting with each other.
,~, The fluorination reactlon ls conducted at an elevated temperature ranglng from 80 to 400C, preferably 100 to 350C
. .. . ..
.:
:
:. : .
... , , .
. .:
and under a slightly lower pressure than atmospheric pressure, preferably -20mm H20.
The fluorinated organic compounds obtained in accordance ~ with the present invention have fluorines in both 1 and 2 positions of their chains.
The quantitative and qualitative analyses of the compounds thus obtaind can be conducted by a gas chromatography, IR spectrometry and NMR method(using H and F19) . to determine their composition.
The following Examples illustrate the present invention more specifically, without limiting the scope of the ;~ invention.
'"' ., Exam~le In a reactor was continuously fed uranium hexafluoride .~ gas as a fluorinating agent at a flow rate of 2.0 kg/hr (5.682 moles/hr) through a spray nozzle. Simultaneously, nitrogen gas was charged into the reactor at a flow rate of 318.1 . Nl/hr(14.2 moles/hr) as a diluent.
, 20 Trichloroethylene was fed into the reactor through ; another spray nozzle while maintaining the molar ratio of . .
trichloroethylene to uranium hexafluoride in the reactor at 1.08:1Ø The fluorination process was carried out as ` follows:
CHCl = CCl2 + UF6 ~ CHClF - CCl2F + UF4 (HCFC-122a) ~ , ' ' . .
'`. ' ' ' 6 ~ ~
Fluorination was carried out at the temperature of 200C and under a pressure of -20mm H20.
The reaction product mixture was passed through the filter made of a porous nickel to remove uranium tetrafluoride dusts and the remaining gas was condensed in a trap cooled with liquid nitrogen to obtain the product as a liquid.
The content of 1,2-difluoro-trichloroethane contained in the organic product was 88.7 wt% and that of 1,1-difluoro-trichloroethane did not exceed 1 wt~.
`~ 10 Exam~le 2 . . .
The procedures described in Example 1 above were repeated , ,.
except that the molar ratio of trichloroethylene to uranium ~;;" 15 hexafluoride was maintained at 1.07:1Ø
: . .
The content of 1,2-difluoro-trichloroethane in the , organic product was 85 wt% and that of 1,1-difluoro-trichloroethane did not exceed 1 wt~.
.
Exam~le 3 ' ..
The procedures described in Example 1 above were repeated except that the molar ratio of trlchloroethylene to uranium ;~ hexafluorlde was malntalned at 1.01:1Ø
The content of 1,2-difluoro-trlchloroethane ln the organlc product was 81 wt~ and that of 1,1-difluoro-. .
i . .
:.-''';
' ''' - ~
,.,' . : - ': : .
.~. . ..
.
:.
: ~ . .
: ' ' : ' ' ' ~lV'165~
: - 7 -~ trichloroethane did not exceed 1 wt~.
.~ Exam~le 4 Similarly to Example 1, the fluorination process was . carried out by using vinylidene chloride as the starting - material as follows:
. . .
CH2 = CCl2 + UF6 ~ CH2F - CCl2F + UF4 (HCFC - 132C) ,'' : The molar ratio of vinylidene chloride to uranium hexa-fluoride was maintained at 1.07:1Ø The fluorination ~i` .
: reaction was carried out at the temperature of 150CC and under .15 a pressure of -20mm H20.
The content of 1,2-difluoro-dichloroethane in the organic .. product was 65 wt% and that of 1,1-difluoro-dichloroethane did :., .,, not exceed 1 wt%.
~;
Exam~le 5 :Similarly to Example 1, the fluorination process was . carried out by uslng vlnyl chlorlde as the starting material as follows:
~' ' : 25 CH2 = CHCl + UF6 ~ CH2F - CHClF + UF4 . (HCFC - 142a) . :
.
~.`.'- , ,. -.: :
: ' .
: ~ .
4 ~ ~ ~
The molar ratio of vinyl chloride to uranium hexafluoride was maintained at 1.06:1Ø The fluorination reaction was :; carried out at the temperature of 120C and under a pressure . of -20mm H20.
: 5 The content of 1,2-difluoro-chloroethane in the organic product was 63 wt% and that of 1,1-difluoro-chloroethane did . not exceed 1 wt%.
. . .
Exam~le 6 . Similarly to Example 1, the fluorination process was carried out by using ethylene as the starting material as ~' follows:
., CH2 = CH2 + VF6 ~ CH2F - CH2F + UF4 (HFC - 152) , The molar ratio of ethylene to uranium hexafluoride was maintained at 1.08:1Ø The reaction was carried out at the . 20 temperature of 100C and under a pressure of -20mm H20.
The content of 1,2-difluoro-ethane in the organic product `~ was 54wt% and that of 1,1-difluoro-ethane did not exceed 1 ," wt%.
'' ,~ 25 ~, : ' :
- . :
,' .
.
:' ' ' , - . :
:, Example 7 '' Similarly to Example 1, the fluorination process was carried out by using vinylidene fluoride as the starting material as follows:
CH2 CF2 + UF6 ~ CH2F - CF3 + UF4 (HFC - 13~a) ..
The molar ratio of vinylidene fluoride to uranium . hexafluoride was maintained at 1.06:1Ø The reaction was `. carried out at the temperature of 350C and under a pressure of -20mm H20.
, The content of 1,1,1,2-tetrafluoroethane in the organic 15 product was 47 wt~ and that of 1,1,2,2--tetrafluoroethane did not exceed 1 wt~.
As shown in the above Examples, in accordance with the present invention, the fluorination of unsaturated ethylenic organic compounds with uranium hexafluoride produces organic : 20 compounds containing fluorines in the 1 and 2 positions of the their chains in surprisinqly high yields, which has not been possible hitherto.
The use of the present method has an added advantage in that it provides a basically wasteless process. The fluoro-. 25 organic isomers obtained have a smaller polarity, and, therefore, a higher solublllty with respect to fats, oils, ' ~ .
' :
'';' 5 ~
`. - 10 -: etc. Besides, the process makes it possible to obtain uranium - tetrafluoride.
While the present invention has been shown and descrlbed with reference to the particular embodiments, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the spirit ... . .
and scope of the invention as defined in the claims.
"
. 10 . . .
' ' : 15 , ., .
;~:
:
, .
:
;.::.
,. .
' ,:, . :
"'-'. ' , ' :, .
. .
The fluorinated organic compounds obtained in accordance ~ with the present invention have fluorines in both 1 and 2 positions of their chains.
The quantitative and qualitative analyses of the compounds thus obtaind can be conducted by a gas chromatography, IR spectrometry and NMR method(using H and F19) . to determine their composition.
The following Examples illustrate the present invention more specifically, without limiting the scope of the ;~ invention.
'"' ., Exam~le In a reactor was continuously fed uranium hexafluoride .~ gas as a fluorinating agent at a flow rate of 2.0 kg/hr (5.682 moles/hr) through a spray nozzle. Simultaneously, nitrogen gas was charged into the reactor at a flow rate of 318.1 . Nl/hr(14.2 moles/hr) as a diluent.
, 20 Trichloroethylene was fed into the reactor through ; another spray nozzle while maintaining the molar ratio of . .
trichloroethylene to uranium hexafluoride in the reactor at 1.08:1Ø The fluorination process was carried out as ` follows:
CHCl = CCl2 + UF6 ~ CHClF - CCl2F + UF4 (HCFC-122a) ~ , ' ' . .
'`. ' ' ' 6 ~ ~
Fluorination was carried out at the temperature of 200C and under a pressure of -20mm H20.
The reaction product mixture was passed through the filter made of a porous nickel to remove uranium tetrafluoride dusts and the remaining gas was condensed in a trap cooled with liquid nitrogen to obtain the product as a liquid.
The content of 1,2-difluoro-trichloroethane contained in the organic product was 88.7 wt% and that of 1,1-difluoro-trichloroethane did not exceed 1 wt~.
`~ 10 Exam~le 2 . . .
The procedures described in Example 1 above were repeated , ,.
except that the molar ratio of trichloroethylene to uranium ~;;" 15 hexafluoride was maintained at 1.07:1Ø
: . .
The content of 1,2-difluoro-trichloroethane in the , organic product was 85 wt% and that of 1,1-difluoro-trichloroethane did not exceed 1 wt~.
.
Exam~le 3 ' ..
The procedures described in Example 1 above were repeated except that the molar ratio of trlchloroethylene to uranium ;~ hexafluorlde was malntalned at 1.01:1Ø
The content of 1,2-difluoro-trlchloroethane ln the organlc product was 81 wt~ and that of 1,1-difluoro-. .
i . .
:.-''';
' ''' - ~
,.,' . : - ': : .
.~. . ..
.
:.
: ~ . .
: ' ' : ' ' ' ~lV'165~
: - 7 -~ trichloroethane did not exceed 1 wt~.
.~ Exam~le 4 Similarly to Example 1, the fluorination process was . carried out by using vinylidene chloride as the starting - material as follows:
. . .
CH2 = CCl2 + UF6 ~ CH2F - CCl2F + UF4 (HCFC - 132C) ,'' : The molar ratio of vinylidene chloride to uranium hexa-fluoride was maintained at 1.07:1Ø The fluorination ~i` .
: reaction was carried out at the temperature of 150CC and under .15 a pressure of -20mm H20.
The content of 1,2-difluoro-dichloroethane in the organic .. product was 65 wt% and that of 1,1-difluoro-dichloroethane did :., .,, not exceed 1 wt%.
~;
Exam~le 5 :Similarly to Example 1, the fluorination process was . carried out by uslng vlnyl chlorlde as the starting material as follows:
~' ' : 25 CH2 = CHCl + UF6 ~ CH2F - CHClF + UF4 . (HCFC - 142a) . :
.
~.`.'- , ,. -.: :
: ' .
: ~ .
4 ~ ~ ~
The molar ratio of vinyl chloride to uranium hexafluoride was maintained at 1.06:1Ø The fluorination reaction was :; carried out at the temperature of 120C and under a pressure . of -20mm H20.
: 5 The content of 1,2-difluoro-chloroethane in the organic product was 63 wt% and that of 1,1-difluoro-chloroethane did . not exceed 1 wt%.
. . .
Exam~le 6 . Similarly to Example 1, the fluorination process was carried out by using ethylene as the starting material as ~' follows:
., CH2 = CH2 + VF6 ~ CH2F - CH2F + UF4 (HFC - 152) , The molar ratio of ethylene to uranium hexafluoride was maintained at 1.08:1Ø The reaction was carried out at the . 20 temperature of 100C and under a pressure of -20mm H20.
The content of 1,2-difluoro-ethane in the organic product `~ was 54wt% and that of 1,1-difluoro-ethane did not exceed 1 ," wt%.
'' ,~ 25 ~, : ' :
- . :
,' .
.
:' ' ' , - . :
:, Example 7 '' Similarly to Example 1, the fluorination process was carried out by using vinylidene fluoride as the starting material as follows:
CH2 CF2 + UF6 ~ CH2F - CF3 + UF4 (HFC - 13~a) ..
The molar ratio of vinylidene fluoride to uranium . hexafluoride was maintained at 1.06:1Ø The reaction was `. carried out at the temperature of 350C and under a pressure of -20mm H20.
, The content of 1,1,1,2-tetrafluoroethane in the organic 15 product was 47 wt~ and that of 1,1,2,2--tetrafluoroethane did not exceed 1 wt~.
As shown in the above Examples, in accordance with the present invention, the fluorination of unsaturated ethylenic organic compounds with uranium hexafluoride produces organic : 20 compounds containing fluorines in the 1 and 2 positions of the their chains in surprisinqly high yields, which has not been possible hitherto.
The use of the present method has an added advantage in that it provides a basically wasteless process. The fluoro-. 25 organic isomers obtained have a smaller polarity, and, therefore, a higher solublllty with respect to fats, oils, ' ~ .
' :
'';' 5 ~
`. - 10 -: etc. Besides, the process makes it possible to obtain uranium - tetrafluoride.
While the present invention has been shown and descrlbed with reference to the particular embodiments, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the spirit ... . .
and scope of the invention as defined in the claims.
"
. 10 . . .
' ' : 15 , ., .
;~:
:
, .
:
;.::.
,. .
' ,:, . :
"'-'. ' , ' :, .
. .
Claims (5)
1. A process for preparing a fluorinated ethanic organic compound, which comprises: reacting ethylene or a halogenated ethylenic compound with uranium hexafluoride at an elevated temperature wherein the molar ratio of ethylene or the halogenated ethylenic compound to uranium hexafluoride ranges from 1:1 to 1.2:1.
2. The process of claim 1 wherein uranium hexafluoride is diluted with an inert gas to a concentration of 20 to 100%
by volume.
by volume.
3. The process of claim 2 wherein the inert gas is selected from the group consisting of nitrogen, neon, argon and fluorinated organic substances recycled from the reaction system.
4. The process of claim 1 wherein the halogenated ethylenic compound is selected from the group consisting of trichloroethylene(C2HCl3), vinylidene chloride(C2H2Cl2), vinyl chloride(C2H3Cl) and vinylidene fluoride(C2H2F2).
5. The process of claim 1 wherein the reaction of ethylene or the halogenated ethylenic compound and uranium hexafluoride is carried out by spraying the each component into the reaction system in a dispersed form and mixing and contacting with each other.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR920015300 | 1992-08-25 | ||
| KR92-15300 | 1992-08-25 |
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| Publication Number | Publication Date |
|---|---|
| CA2104654A1 true CA2104654A1 (en) | 1994-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002104654A Abandoned CA2104654A1 (en) | 1992-08-25 | 1993-08-23 | Process for the preparation of fluorinated ethanic compounds |
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| Country | Link |
|---|---|
| JP (1) | JPH06219976A (en) |
| KR (1) | KR960008639B1 (en) |
| CN (1) | CN1085538A (en) |
| CA (1) | CA2104654A1 (en) |
| DE (1) | DE4328606C2 (en) |
| ES (1) | ES2072817B1 (en) |
| FR (1) | FR2695123B1 (en) |
| GB (1) | GB2271989B (en) |
| IT (1) | IT1287886B1 (en) |
| MX (1) | MX9305161A (en) |
| TW (1) | TW232680B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB0021618D0 (en) | 2000-09-02 | 2000-10-18 | Ici Plc | Production of hydrofluoroalkanes |
| JP7166889B2 (en) * | 2018-11-20 | 2022-11-08 | ダイキン工業株式会社 | Method for producing 1,2-difluoroethylene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3235608A (en) * | 1962-03-19 | 1966-02-15 | Du Pont | Fluorination with uranium hexafluoride |
| US3382049A (en) * | 1965-01-27 | 1968-05-07 | Nuclear Materials & Equipment | Method for producing uranium tetrafluoride |
| US3413099A (en) * | 1966-11-14 | 1968-11-26 | United Nuclear Corp | Production of uranium tetrafluoride |
| GB9105167D0 (en) * | 1991-03-12 | 1991-04-24 | Ici Plc | Chemical process |
-
1993
- 1993-08-10 KR KR93015487A patent/KR960008639B1/en active IP Right Grant
- 1993-08-21 TW TW082106756A patent/TW232680B/zh active
- 1993-08-23 CA CA002104654A patent/CA2104654A1/en not_active Abandoned
- 1993-08-23 JP JP5207620A patent/JPH06219976A/en active Pending
- 1993-08-23 ES ES09301849A patent/ES2072817B1/en not_active Expired - Lifetime
- 1993-08-24 IT IT93MI001843A patent/IT1287886B1/en active IP Right Grant
- 1993-08-24 FR FR9310208A patent/FR2695123B1/en not_active Expired - Fee Related
- 1993-08-24 GB GB9317591A patent/GB2271989B/en not_active Expired - Fee Related
- 1993-08-25 CN CN93116782A patent/CN1085538A/en active Pending
- 1993-08-25 MX MX9305161A patent/MX9305161A/en unknown
- 1993-08-25 DE DE4328606A patent/DE4328606C2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR940003903A (en) | 1994-03-14 |
| GB9317591D0 (en) | 1993-10-06 |
| ITMI931843A0 (en) | 1993-08-24 |
| ITMI931843A1 (en) | 1995-02-24 |
| DE4328606A1 (en) | 1994-03-03 |
| TW232680B (en) | 1994-10-21 |
| KR960008639B1 (en) | 1996-06-28 |
| MX9305161A (en) | 1994-02-28 |
| ES2072817B1 (en) | 1996-02-16 |
| ES2072817A1 (en) | 1995-07-16 |
| FR2695123B1 (en) | 1994-10-28 |
| GB2271989B (en) | 1995-10-11 |
| JPH06219976A (en) | 1994-08-09 |
| DE4328606C2 (en) | 1996-05-02 |
| CN1085538A (en) | 1994-04-20 |
| GB2271989A (en) | 1994-05-04 |
| IT1287886B1 (en) | 1998-08-26 |
| FR2695123A1 (en) | 1994-03-04 |
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