WO1994029251A1 - Procede de production de 1,1,1,3,3-pentafluoropropane et/ou de 1,1,3,3,3-pentafluoropropene - Google Patents
Procede de production de 1,1,1,3,3-pentafluoropropane et/ou de 1,1,3,3,3-pentafluoropropene Download PDFInfo
- Publication number
- WO1994029251A1 WO1994029251A1 PCT/JP1994/000865 JP9400865W WO9429251A1 WO 1994029251 A1 WO1994029251 A1 WO 1994029251A1 JP 9400865 W JP9400865 W JP 9400865W WO 9429251 A1 WO9429251 A1 WO 9429251A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- reaction
- catalyst
- production method
- pentafluoropropene
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 230000002829 reductive effect Effects 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000006298 dechlorination reaction Methods 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- KBLCTGKKNBQHOP-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-9h-fluorene Chemical compound C1C(C(=C(F)C(F)=C2F)F)=C2C2=C1C=CC=C2F KBLCTGKKNBQHOP-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- YTCHAEAIYHLXBK-UHFFFAOYSA-N 2-chloro-1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=C(Cl)C(F)(F)F YTCHAEAIYHLXBK-UHFFFAOYSA-N 0.000 abstract description 6
- XAHBEACGJQDUPF-UHFFFAOYSA-N 1,2-dichloro-1,1,3,3,3-pentafluoropropane Chemical compound FC(F)(F)C(Cl)C(F)(F)Cl XAHBEACGJQDUPF-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000382 dechlorinating effect Effects 0.000 abstract description 3
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010574 gas phase reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- JRHNUZCXXOTJCA-UHFFFAOYSA-N 1-fluoropropane Chemical compound CCCF JRHNUZCXXOTJCA-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000004604 Blowing Agent Substances 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000008429 bread Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 1
- QBDGVDHPRSZFHW-UHFFFAOYSA-N 1,1,1,3,3-pentachloro-2-fluoropropane Chemical compound ClC(Cl)C(F)C(Cl)(Cl)Cl QBDGVDHPRSZFHW-UHFFFAOYSA-N 0.000 description 1
- GSUYOAATQQUQDM-UHFFFAOYSA-N 1,2-dichloro-3-fluoropropane Chemical compound FCC(Cl)CCl GSUYOAATQQUQDM-UHFFFAOYSA-N 0.000 description 1
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 1
- BNUSKMGXRXIWAF-UHFFFAOYSA-N 3-chloro-1,1,1,3-tetrafluorobutane Chemical compound CC(F)(Cl)CC(F)(F)F BNUSKMGXRXIWAF-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
Definitions
- the present invention uses CFC or HC as refrigerant, mk washing ⁇ I
- a method for producing 1,1,1,3,3-pentafluoroprop mouth bread is as follows: 1,2,3-trichloromouth 1,1,1,3,3-pentafluoropropane is used as a raw material and a palladium catalyst is used. There is known a method of performing hydrogen reduction using thiophene (US Pat. No. 2,942,036).
- 1,1,3,3,3-pentafluoropropene is a useful compound that can be used not only as a raw material for HFC blowing agents that do not destroy the ozone layer, but also as a raw material for various resins or drug intermediates. It is.
- a method of decarboxylation of ⁇ -hydroperfluoroisobutyrate potassium salt is also known, but this method not only makes it difficult to obtain raw materials but also industrially performs a decarboxylation reaction. (Synthesis of Fluoroorganic Compounds, IL Knunyants and GG Yakobson, Springer—Verlag, Berlin, Heidelberg, P8 (1985)).
- An object of the present invention is to provide a production method for obtaining 1,1,1,3,3-bentafluorop ⁇ -pan with high yield from 1,1,3,3,3-pentafluo ⁇ -propene as a raw material. It is in.
- Another object of the present invention is to produce 2-chloro-1,1,3,3,3-pentafluoropropene as a raw material and obtain 1,1,1,3,3-pentafluorofluoride in good yield.
- the object of the present invention is to provide a manufacturing method for obtaining rob mouth bread and Z or 1,1,1,3,3,3-pentafluoropropene.
- Still another object of the present invention is to use 1,1,1,3,3-pentafluoro-2,3-dichloropipropane as a raw material and to be industrially feasible for 1,1,3,3.
- An object of the present invention is to provide a production method capable of easily obtaining 3-pentafluoropropene.
- the present inventor provides a method for producing 1,1,1,3,3-pentafluoropropane using 1,1,3,3,3-pentafluoropropene as a raw material by a hydrogenation reaction in a gas phase method.
- the reaction rate decreases when 1,1,3,3,3-pentapentafluorobutene pen is hydrogenated at room temperature in the presence of a palladium catalyst as in the past, while the reaction rate decreases when the reaction rate is increased.
- the desired product could be obtained at a high yield, and completed the first invention.
- activated carbon was used as the carrier for the palladium catalyst, the selectivity would be 100%.
- the gist of the first invention is that a 1,1,3,3,3-pentafluorob ⁇ pen is used as a raw material and a 7j element addition reaction is carried out at 40 to 300 in the presence of a palladium catalyst to obtain a 99
- the reaction i3 ⁇ 4g is 40 to 300 in order to realize the above-mentioned object. That is, if the reaction is less than 40C, the reaction rate is lowered, and if it exceeds 300, by-products are generated and the equipment parts used are easily damaged.
- the reaction is preferably between 50 and 200.
- the method of the gas phase reaction according to the first invention is a fixed bed type gas phase reaction, m
- a system such as a bed-type gas phase reaction can be used.
- the palladium catalyst used in the method of the first invention can be used by being supported on a carrier comprising at least one selected from activated carbon, silica gel, titanium oxide and zirconia. Those are preferred.
- the particle size of the carrier has little effect on the reaction, but is preferably 0.1 to 100: 3 mm.
- the loading concentration a wide range of 0.05 to 10% by weight can be used, but a loading of 0.5 to 5% by weight is usually recommended.
- the ratio of hydrogen to raw material can vary greatly.
- hydrogenation is usually carried out using at least a stoichiometric amount of hydrogen.
- stoichiometric amount for example 5 times or more hydrogen, can be used relative to the total moles of starting material. Excess hydrogen can be recovered and reused.
- the reaction is not particularly limited and can be performed under increased pressure, reduced pressure, or normal pressure. However, it is preferable to perform the reaction under increased pressure or normal pressure.
- the contact time is usually 0.1 to 300 seconds, preferably 1 to 30 seconds.
- 1,1,3,3,3-Pentafluoropropene which is a raw material used in the reaction of the first invention, is, for example, 2,3-dichloro-1,1,1,3,3- It is obtained by dechlorinating Pennofluorpropane with metallic zinc. 2,3-Dichloro-1,1,1,3,3- ⁇ pentafluoropropane was heated to reflux with 1.5 equivalents of metallic zinc in ethanol and heated to reflux. By dropping 3-dichloro-1,1,1,3,3-pentanofluoropropane, 1,1,3,3,3-pentafluoropropene was obtained with a yield of 90%.
- the present inventors have conducted intensive studies on the production methods of 1,1,1,3,3-pentafluoropropane and 1,1,3,3,3-pentafluoropropene, and as a result, have found that Mouth-1,1,8,3,3-pentanofluorob If hydrogenation is performed by gas-phase method using a pen as a raw material in the presence of palladium, platinum and rhodium catalysts, the desired product can be obtained in high yield. And completed the second invention.
- the gist of the second invention is the existence of a catalyst comprising at least one selected from palladium, platinum and rhodium, using 2-chloro-1,1,3,3,3-pentafluoropropene as a raw material.
- a catalyst comprising at least one selected from palladium, platinum and rhodium, using 2-chloro-1,1,3,3,3-pentafluoropropene as a raw material.
- a method of the gas phase reaction according to the second invention a method such as a fixed bed type gas phase reaction and a fluidized bed type gas phase reaction can be adopted.
- the catalyst comprising at least one selected from palladium, platinum and rhodium is preferably a catalyst supported on a carrier comprising at least one selected from activated carbon, alumina, silica gel, titanium oxide, zirconia and others.
- the loading concentration a wide range of 0.05 to 10% by weight can be used, but usually 0.5 to 5% by weight is recommended.
- the reaction is usually 30-450. C, preferably 70-400.
- the ratio of hydrogen to raw material can vary greatly.
- hydrogen sulfide is performed using at least a stoichiometric amount of hydrogen.
- stoichiometric amounts for example 5 times or more hydrogen, can be used relative to the total moles of starting material.
- the pressure of the reaction is not particularly limited, and the reaction can be performed under increased pressure, reduced pressure, or normal pressure. However, the reaction is preferably performed under increased pressure or normal pressure.
- the contact time is usually 0.1 to 300 seconds, preferably 1 to 30 seconds.
- the raw material used in this reaction is, for example, 2,2-dichloro-1,1,1 Dehydrochlorination of, 3,3-Pennofluorop ⁇ -pan gives a good yield.
- the reaction temperature is preferably 0 to 100 ° C.
- the alkali concentration is preferably 10-70%.
- the pressure for the reaction is not particularly limited and can be increased under pressure, reduced pressure, or normal pressure. However, it is preferable to perform the reaction under increased pressure or normal pressure.
- 1,1,3,3,3-pentafluoropropene obtained by this reaction is quantitatively reacted by a gas phase method using a palladium catalyst (in particular, the reaction of the first invention described above).
- 1,1,1,3,3-pentachlorofluoropropane can be produced directly from the starting materials.
- the present inventor has further conducted intensive studies on an efficient and inexpensive production process of 1,1,3,3,3-pentanofluoropropene, and as a result, can obtain a cheaper 1,1,1,3,3.
- the gist of the third invention is that 1,1,1,3,3- In this method, 1,1,3,3,3-pentylfluoropropene is obtained by dechlorinating 2,3-diglolobane with hydrogen in the presence of a metal oxide catalyst.
- the raw material 1,1,1,3,3-pentafluoro-2,3-dichloropropane is obtained by subjecting hexaclopropene to fluorination reaction with HF in the presence of a halogenated antimony. Can be obtained easily.
- the metal oxide used as a catalyst is iron, chromium, cobalt, copper, It is preferably an oxide of at least one metal selected from nickel and manganese.
- These metal oxide catalysts are prepared by adding an aqueous ammonia solution or alkali metal hydroxide to an aqueous solution of chloride, sulfate, or nitrate of Cr, Fe, Co, Cu, Ni, or Mn by a general method. In addition, it can be obtained by calcining the precipitated metal hydroxide. These can be used alone, but a composite oxide or a mixed oxide of a plurality of metals selected from these metals can also be used for the reaction.
- These metal oxides may be granulated or may be compressed into pellets.
- these may be supported on a carrier which does not directly participate in the reaction, for example, at least one carrier selected from activated carbon, alumina, aluminum fluoride, silica gel, calcium fluoride and the like.
- a carrier which does not directly participate in the reaction
- at least one carrier selected from activated carbon, alumina, aluminum fluoride, silica gel, calcium fluoride and the like.
- These metal oxides may be reduced to zero during pretreatment with 7j element or during the reaction, and may become zero-valent.
- the reaction can be carried out if the excess amount of 7j element is at least 1 mol of the starting material required for the reaction, but it is practically preferable to carry out the reaction at 1.5 mol or more. Also, excess Hydrogen shortens the contact time and reduces the conversion of the reaction.
- the reaction temperature in the reductive dehalogenation may be in the range of 200 to 400, and can be appropriately selected depending on the activity of the catalyst. As is generally known, increasing the reaction temperature increases the reaction rate. Therefore, when a catalyst with low activity is used, a higher reaction is used. However, when it exceeds 400, the ratio of C 2 and C 4 compounds, which are thought to be formed by the cleavage and bonding of carbon-carbon bonds, increases, and the selectivity decreases.
- the contact time can be appropriately selected according to the catalytic activity and the conversion rate desired in the reaction. Generally, when the catalytic activity is low, the contact time can be extended to set an appropriate conversion.
- the present invention relates to the above-mentioned 1, 1, 1, 3, 3-pentafluoro 2,
- 3-Dichloropropane is dechlorinated with hydrogen in the presence of a metal oxide catalyst, and then the resulting 1,1,3,3,3-pentafluoropropene is purified in the presence of a palladium catalyst. It is characterized by reacting with hydrogen by a gas phase method.
- a method for producing 1,1,3,3-pentafluoropropane is also included in the fourth invention.
- the metal oxide catalyst and its carrier, the amount of hydrogen used, and the dechlorination reaction temperature are desirably the same as those applied in the third invention.
- 1,1,3,3,3-pentafluoropropene is reacted with hydrogen by a gas phase method in the presence of a palladium catalyst, and hydrogen is reduced in a temperature range of 40 to 300.
- 1, 1, 1, 3, 3 Fluoropropane can be manufactured.
- 2-chloro-1,1,3,3,3-pentanofluoride ⁇ pen is used as a raw material in the presence of a catalyst comprising at least one selected from palladium, platinum and rhodium.
- hydrogenation is carried out at ⁇ 3 ⁇ 4 of 30 to 450, so that 1,1,1,3,3-pentafluoropropane and ⁇ or 1,1,3,3,3-pentafluorolob ⁇ ⁇ Can be manufactured.
- 1,1,1,3,3-pentafluoro-2,3 dichloropropane is dechlorinated with hydrogen in the presence of a metal oxide catalyst.
- 3, 3-bentafluoropropene can be produced with high selectivity.
- this 1,1,3,3,3-pentafluoropropene is reacted with hydrogen in a gas phase method in the presence of a palladium catalyst to produce 1,1,1,3,3-pentafluoropropene. Can lead to fluoropropane.
- 1,1,1,3,3-Pentafluorobroban obtained by the present invention is a useful compound that can be a substitute for CFC and HCFC used as a refrigerant, a blowing agent, and a washing agent.
- 1,1,3,3,3-pentafluoropipropene can be easily derived into 1,1,1,3,3-pentafluoropropane by addition of 7j element, and the monomer of high molecular compound can be easily derived. It is also useful as an intermediate for other fluorine-containing organic compounds.
- Example 2 The same reactor as in Example 1 was filled with 2.3 cc of a palladium catalyst supported on activated carbon at a concentration of 0.5%. After that, 1,1,3,3,3-pentafluorob pen was introduced at a rate of 5.5 cc / min, and 7J element was introduced at a rate of 14.5 cc / min. Reaction ⁇ 1 ⁇ 2 was performed at 50. The generated gas was analyzed by gas chromatography after washing 7j. The results are shown in Table 1.
- Example 2 The same reactor as in Example 1 was charged with 1.9 cc of a palladium catalyst supported on alumina at a concentration of 0.5%, and the temperature was raised to room temperature (23 ° C) while flowing nitrogen gas. A 3,3-pentafluorov pen was introduced at a rate of 5.5 ccZ, and hydrogen was introduced at a rate of 14.5 ccZ. Reaction i3 ⁇ 4g 23. C went. The generated gas was analyzed by gas chromatography after washing with water. The desired 1,1,1,3,3-pentafluoropropane was obtained with a conversion of 75.3% and a selectivity of 99.9%.
- the target product can be obtained with a high reaction rate and a high selectivity based on the method of the first invention.
- Example 3 The same reactor as in Example 3 was filled with 18 cc of a palladium catalyst supported on a carbon pellet at a concentration of 0.5%, and heated to 250 in a furnace while flowing nitrogen gas, and after reaching a predetermined value, , 2-Chloro-1,1,3,3,3-pentafluoro ⁇ -propene was vaporized in advance and converted to gas. cc and hydrogen were introduced at a rate of 136.8 ccZ. The reaction temperature was 250. The generated gas was washed with water, dried over calcium chloride, and analyzed by gas chromatography. The results are shown in Table 2.
- the C r (N 0 8) s ⁇ 9 H 2 0 of 120g was dissolved in water 250Ral, while stirring and an aqueous solution 200ml of this and 28 hydroxide Anmoniumu, were added to water heated 4 100 ml, A precipitate of hydroxide was obtained. This was separated by filtration, washed with pure water, and dried, and then calcined at 450 for 5 hours to obtain an oxide (chromium oxide) powder. This was molded into a cylinder 5 mm in diameter and 5 ran in height using a tableting machine.
- Hastelloy C reaction tube ( ⁇ 20 sq. X 1000 sq.) was filled with 10 g of the above chromium oxide powder and set for the reaction. Pretreatment was performed by flowing 7j element in advance at 200ral / min for 3 hours. Thereafter, 50 ml / rain of 1,1,1,3,3-pentene fluoro-2,3-dichloropropane was flowed. After the gas was washed with water, it was analyzed by gas chromatography. (Selectivity, anti) »was determined by multiplying the peak area of the gas chromatograph by the correction factor separately obtained. Table 3 shows the results.
- the main by-product was 1,1,1,3-tetrafluoro-3-chlorobutane.
- the target product (1,1,3,3 , 3-Ventafluoroproben) was obtained with high selectivity.
- the main by-product was 1,1,1,3-tetrafluoro-3-chloroprobe, but the target product was obtained with high selectivity in this example as well.
- Ni ( ⁇ 0 8) 2 ⁇ 6H 2 0 of 87g was dissolved in water of 250 ml, and dried by adding silica force gel 181 g thereto. This was heated to 400 to obtain nickel oxide. This was molded into a cylinder with a diameter of 5 rara and a height of 5 mm using a tableting machine.
- a reaction tube made of Hastelloy C ( ⁇ 20 xiOOOrara) was filled with 10 g of the above catalyst, and this was set as reaction II. Pretreatment was performed by flowing hydrogen at 200 ml / rain for 3 hours in advance. Thereafter, 1,1,1,3,3-pentafluoro-2,3-dichloropropane was flowed at 50 ml / min. The generated gas was washed with water and analyzed by gas chromatography. The selectivity and the reaction rate were obtained by multiplying the peak area of the gas chromatograph by the correction coefficient separately obtained. The results are shown in Table 6.
- the main by-product is 1,1,1,3-tetrafluoro-3-chloropi probe.
- the desired product was obtained with a low selectivity.
- the Cr ( ⁇ 0 8) 3 ⁇ 9H 2 0 of 120g was dissolved in water of 250 ml, was dried by adding thereto shea Rikageru 181 g. This was heated to 400 to obtain nickel oxide. This was molded into a cylindrical shape with a diameter of 5 cm and a height of 5 mm using a tableting machine.
- Hastelloy C reaction tube ( ⁇ 20 Cheom X1000 Sir) was filled with 10 g of the above catalyst, and this was set for the reaction. Pretreatment was performed by flowing hydrogen at 200 ral / min for 3 hours in advance. Thereafter, 50 ml / min of 1,1,1,3,3-pentafluoro-2,3-dichlorobroban was flowed. The generated gas was washed with water and analyzed by gas chromatography. The selectivity and the reaction rate were obtained by multiplying the peak area of the gas chromatograph by the correction coefficient separately obtained. Table 7 shows the results.
- the main by-product was 1,1,1,3-tetrafluoro-3-chloro- ⁇ -probe, but the target product was obtained with high selectivity in this example as well.
- Example 11
- the main by-product is 1,1,1,3-tetrafluoro-3-chlorochlorobenzene
- the desired product was obtained with high selectivity.
Description
Claims
Priority Applications (3)
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EP94916420A EP0703207B1 (en) | 1993-06-10 | 1994-05-30 | Process for producing 1,1,1,3,3-pentafluoropropane and/or 1,1,3,3,3-pentafluoropropene |
US08/549,816 US5714654A (en) | 1993-06-10 | 1994-05-30 | Method of Producing 1,1,1,3,3-pentafluoropropane and/or 1,1,3,3,3-pentafluoropropene |
DE69422812T DE69422812T2 (de) | 1993-06-10 | 1994-05-30 | Verfahren zur herstellung von 1,1,1,3,3-pentafluorpropan und/oder 1,1,3,3,3-pentafluorpropen |
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JP5/165230 | 1993-06-10 | ||
JP16523093 | 1993-06-10 | ||
JP35163393A JP3407379B2 (ja) | 1993-06-10 | 1993-12-29 | 1,1,1,3,3−ペンタフルオロプロパンの製造方法 |
JP5/351633 | 1993-12-29 |
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PCT/JP1994/000865 WO1994029251A1 (fr) | 1993-06-10 | 1994-05-30 | Procede de production de 1,1,1,3,3-pentafluoropropane et/ou de 1,1,3,3,3-pentafluoropropene |
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US (1) | US5714654A (ja) |
EP (3) | EP0885862B1 (ja) |
JP (1) | JP3407379B2 (ja) |
DE (2) | DE69422812T2 (ja) |
WO (1) | WO1994029251A1 (ja) |
Cited By (4)
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EP0737661A1 (en) * | 1995-04-14 | 1996-10-16 | Asahi Glass Company Ltd. | Method for producing 1,1,1,3,3-Pentafluoropropane |
US6023004A (en) * | 1996-11-12 | 2000-02-08 | Alliedsignal, Inc. | Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon |
US6476281B2 (en) | 1999-04-05 | 2002-11-05 | Pcbu Services, Inc. | Method for the preparation of 1,1,1,3,3-pentafluoropropene and 1,1,1,3,3-pentafluoropropane |
US7288211B2 (en) | 1999-03-15 | 2007-10-30 | Honeywell International Inc. | Hydrofluorocarbon blown foam and method for preparation thereof |
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JP3500617B2 (ja) * | 1993-08-27 | 2004-02-23 | ダイキン工業株式会社 | ヘキサフルオロシクロブタンの製造方法 |
US5945573A (en) * | 1997-01-31 | 1999-08-31 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 1,1,1,3,3-pentafluoropropane |
EP1043297B8 (en) * | 1997-12-26 | 2005-09-07 | Zeon Corporation | Process for the preparation of compounds having -ch2-chf- groups |
US7091388B2 (en) * | 2003-09-26 | 2006-08-15 | Honeywell International Inc. | Method of making 1,1,3,3,3-pentafluoropropene |
WO2007056128A1 (en) | 2005-11-03 | 2007-05-18 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
RU2469016C2 (ru) * | 2007-02-06 | 2012-12-10 | Солвей Флуор Гмбх | Невоспламеняющиеся композиции, содержащие фторированные соединения, и применение этих композиций |
US8287579B2 (en) * | 2007-09-17 | 2012-10-16 | Thermage, Inc. | Method of using cryogenic compositions for cooling heated skin |
US8044250B2 (en) * | 2007-11-16 | 2011-10-25 | Honeywell International Inc. | Manufacture of 1,1,1,2,3,3-hexafluoropropane and 1,1,1,2-tetrafluoropropane via catalytic hydrogenation |
GB0801209D0 (en) * | 2008-01-23 | 2008-02-27 | Ineos Fluor Holdings Ltd | Process |
EP2443128B1 (en) * | 2009-06-19 | 2017-12-20 | LEK Pharmaceuticals d.d. | New synthetic route for the preparation of alpha-amino boronic esters |
TW201204685A (en) | 2010-06-23 | 2012-02-01 | Asahi Glass Co Ltd | Process for Producing 2, 3, 3, 3-Tetrafluoropropene |
WO2011162340A1 (ja) | 2010-06-23 | 2011-12-29 | 旭硝子株式会社 | 2,3,3,3-テトラフルオロプロペンの製造方法 |
TW201247315A (en) * | 2011-05-16 | 2012-12-01 | Du Pont | Catalytic hydrogenation of fluoroolefins, alpha-alumina supported palladium compositions and their use as hydrogenation catalysts |
US9290424B2 (en) * | 2013-03-14 | 2016-03-22 | Honeywell International Inc. | Processes for the hydrogenation of halogenated alkenes and the manufacture of fluorinated olefins |
CN106316775A (zh) * | 2016-08-22 | 2017-01-11 | 巨化集团技术中心 | 一种 1,1,1,4,4,4‑六氟‑2‑丁烯的制备方法 |
JP7348535B2 (ja) * | 2021-07-15 | 2023-09-21 | ダイキン工業株式会社 | アルケンの製造方法 |
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-
1993
- 1993-12-29 JP JP35163393A patent/JP3407379B2/ja not_active Expired - Fee Related
-
1994
- 1994-05-30 DE DE69422812T patent/DE69422812T2/de not_active Expired - Fee Related
- 1994-05-30 EP EP98114339A patent/EP0885862B1/en not_active Expired - Lifetime
- 1994-05-30 DE DE69431853T patent/DE69431853T2/de not_active Expired - Fee Related
- 1994-05-30 EP EP98114340A patent/EP0882693A1/en not_active Ceased
- 1994-05-30 WO PCT/JP1994/000865 patent/WO1994029251A1/ja active IP Right Grant
- 1994-05-30 EP EP94916420A patent/EP0703207B1/en not_active Expired - Lifetime
- 1994-05-30 US US08/549,816 patent/US5714654A/en not_active Expired - Fee Related
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JPH01146831A (ja) * | 1987-10-20 | 1989-06-08 | Bayer Ag | フツ素化c↓4〜c↓6炭化水素の製造方法 |
JPH02129131A (ja) * | 1988-11-08 | 1990-05-17 | Asahi Glass Co Ltd | 1,1,2,2―テトラフルオロエタンの製造方法 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0737661A1 (en) * | 1995-04-14 | 1996-10-16 | Asahi Glass Company Ltd. | Method for producing 1,1,1,3,3-Pentafluoropropane |
US5663464A (en) * | 1995-04-14 | 1997-09-02 | Asahi Glass Company Ltd. | Method for producing1,1,1,3,3-pentafluoropropane |
US6023004A (en) * | 1996-11-12 | 2000-02-08 | Alliedsignal, Inc. | Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon |
US6689924B1 (en) | 1996-11-12 | 2004-02-10 | Honeywell International Inc. | Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon |
US7288211B2 (en) | 1999-03-15 | 2007-10-30 | Honeywell International Inc. | Hydrofluorocarbon blown foam and method for preparation thereof |
US6476281B2 (en) | 1999-04-05 | 2002-11-05 | Pcbu Services, Inc. | Method for the preparation of 1,1,1,3,3-pentafluoropropene and 1,1,1,3,3-pentafluoropropane |
US6583328B1 (en) | 1999-04-05 | 2003-06-24 | Pcbu Services, Inc. | Method for the preparation of 1,1,1,3,3-pentafluoropropene and 1,1,1,3,3-pentafluoropropane |
Also Published As
Publication number | Publication date |
---|---|
DE69431853D1 (de) | 2003-01-16 |
DE69422812D1 (de) | 2000-03-02 |
EP0703207A1 (en) | 1996-03-27 |
DE69431853T2 (de) | 2003-09-11 |
EP0703207B1 (en) | 2000-01-26 |
JPH0769943A (ja) | 1995-03-14 |
EP0885862A1 (en) | 1998-12-23 |
EP0885862B1 (en) | 2002-12-04 |
DE69422812T2 (de) | 2000-10-12 |
JP3407379B2 (ja) | 2003-05-19 |
US5714654A (en) | 1998-02-03 |
EP0703207A4 (en) | 1996-10-02 |
EP0882693A1 (en) | 1998-12-09 |
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