EP2903960A1 - Method for processing fluoric acid - Google Patents
Method for processing fluoric acidInfo
- Publication number
- EP2903960A1 EP2903960A1 EP13762846.7A EP13762846A EP2903960A1 EP 2903960 A1 EP2903960 A1 EP 2903960A1 EP 13762846 A EP13762846 A EP 13762846A EP 2903960 A1 EP2903960 A1 EP 2903960A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- process according
- fluorinated
- solvent
- aqueous solution
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title abstract description 3
- 229960002050 hydrofluoric acid Drugs 0.000 title abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 77
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003960 organic solvent Substances 0.000 claims abstract description 46
- 150000003839 salts Chemical class 0.000 claims abstract description 44
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000012429 reaction media Substances 0.000 claims abstract description 12
- 230000003381 solubilizing effect Effects 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 claims description 16
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001243 acetic acids Chemical class 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000005215 alkyl ethers Chemical class 0.000 claims description 9
- 239000003849 aromatic solvent Substances 0.000 claims description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- -1 mesithylene Chemical compound 0.000 claims description 7
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000002051 biphasic effect Effects 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007701 flash-distillation Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229940117389 dichlorobenzene Drugs 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims description 4
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000012454 non-polar solvent Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 14
- 239000008346 aqueous phase Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 239000002609 medium Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000010908 decantation Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229940078552 o-xylene Drugs 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 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 3
- 238000004458 analytical method Methods 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- MHAIQPNJLRLFLO-UHFFFAOYSA-N methyl 2-fluoropropanoate Chemical compound COC(=O)C(C)F MHAIQPNJLRLFLO-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- OYGXDHKBZYCDGG-UHFFFAOYSA-M potassium;2,2-difluoroacetate Chemical compound [K+].[O-]C(=O)C(F)F OYGXDHKBZYCDGG-UHFFFAOYSA-M 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- PFYAMVWLZDZJOQ-UHFFFAOYSA-M sodium;2,2-difluoroacetate Chemical compound [Na+].[O-]C(=O)C(F)F PFYAMVWLZDZJOQ-UHFFFAOYSA-M 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- ZVZPFTCEXIGSHM-UHFFFAOYSA-N 2-fluoropropanoic acid Chemical compound CC(F)C(O)=O ZVZPFTCEXIGSHM-UHFFFAOYSA-N 0.000 description 1
- KSNKQSPJFRQSEI-UHFFFAOYSA-M 3,3,3-trifluoropropanoate Chemical compound [O-]C(=O)CC(F)(F)F KSNKQSPJFRQSEI-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 229910001119 inconels 625 Inorganic materials 0.000 description 1
- 229910000816 inconels 718 Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 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 description 1
- 238000005259 measurement Methods 0.000 description 1
- RDOXTESZEPMUJZ-WBJZHHNVSA-N methoxybenzene Chemical group CO[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 RDOXTESZEPMUJZ-WBJZHHNVSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- JPLXPYOYBYIHKN-UHFFFAOYSA-M potassium;3,3,3-trifluoropropanoate Chemical compound [K+].[O-]C(=O)CC(F)(F)F JPLXPYOYBYIHKN-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
- C07C51/493—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification whereby carboxylic acid esters are formed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Definitions
- the present invention relates to a process for the treatment of fluorinated acid, in particular of fluorinated acetic acid, for example difluoroacetic acid (DFA) or trifluoroacetic acid (TFA), in particular a process for the treatment of fluorinated acid under salified form in an aqueous solution.
- fluorinated acid in particular of fluorinated acetic acid, for example difluoroacetic acid (DFA) or trifluoroacetic acid (TFA)
- DFA difluoroacetic acid
- TSA trifluoroacetic acid
- DFA can be produced by different processes and according to the process can be solubilized in an aqueous solution in the form of a salt, especially sodium salt. DFA, even after acidification, is soluble in aqueous solution; this makes its recovery, for example by distillation or extraction, very difficult.
- the object of the present invention is to provide a process for the treatment of fluorinated acid, in particular a process for treating a fluorinated acid salt in aqueous solution, in particular DFA or TFA.
- Another object of the present invention is to provide such a method which is simple to implement and which makes it possible to obtain a product that can be recovered in good yields and with high purity.
- the method of the present invention makes it possible to remedy the various problems mentioned above.
- the inventors have surprisingly discovered that it is possible to treat an aqueous solution containing a fluorinated acid salt soluble in aqueous phase, by esterification of this salt in acidic medium.
- the method of the invention also solves this technical problem.
- the present invention relates to a method for treating an aqueous solution comprising a salt of an organic compound comprising at least one acid function and at least one fluorine atom, said fluoro acid, by reaction between said salt and at least one Brönsted acid in the presence of an organic solvent solubilizing the product that is formed, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution.
- the fluorinated acid is especially chosen from fluorinated carboxylic acids soluble in water.
- the acid is chosen from aliphatic carboxylic acids comprising at least one fluorine atom and comprising from 2 to 15 carbon atoms, preferably from 2 to 10 carbon atoms.
- aliphatic carboxylic acids comprising at least one fluorine atom and comprising from 2 to 15 carbon atoms, preferably from 2 to 10 carbon atoms.
- fluorinated acetic acids mention may be made.
- fluoroacetic acid is intended to denote mono-, di- and trifluoroacetic acids, and any of their mixtures, preferably di- and trifluoroacetic acids, more particularly the difluoroacetic acid.
- the aqueous solution comprising the fluorinated acid salt is an aqueous solution from a process for preparing said acid.
- the aqueous solution comprising the fluorinated acid salt is an effluent, the fluorinated acid then being a by-product to be upgraded.
- the counterion may in particular be chosen from the elements of columns 1 to 12 of the periodic table of the elements, preferably the counterion is an alkaline or an alkaline earth metal, for example sodium, potassium or lithium.
- the choice of the organic solvent among the abovementioned solvents is then carried out as a function of the density of the aqueous medium comprising the salt of the salified fluorinated acid.
- the term "at least one biphasic liquid / liquid reaction medium” denotes a medium comprising two liquid phases, on the one hand the organic solvent phase and, on the other hand, the aqueous phase, such a medium may also comprise suspended solid compounds. such as, for example, precipitated salts.
- the term "Brönsted acid” means a molecule capable of yielding one or more protons.
- a Brönsted acid according to the invention is chosen from strong acids whose pKa is less than 2, and in particular from HCl, H 2 SO 4 , HNO 3 , HBr or H 3 PO 4 , pure or diluted, or any of their mixtures.
- Hydrochloric acid can be used in gaseous form and / or in solution (aqueous solution).
- the acid is used in proportions of 1 to 5 molar equivalents, preferably 1 to 3 molar equivalents, relative to the salt of the fluorinated acid.
- the product formed from the reaction between the fluorinated acid salt and the Brönsted acid is solubilized by the organic solvent.
- the organic solvent can be used in any proportion; it is preferably used in proportions of 50 to 200%, preferably 50 to 100% by volume relative to the volume of the aqueous solution.
- the process of the invention can be carried out at a temperature of 10 to
- the method of the invention is implemented in batch. In another particular embodiment, the method of the invention is implemented continuously.
- a reactor provided with a stirring system that allows a strong stirring of the reaction medium, in particular a reactor equipped with a type 4 stirring system.
- blades in particular four inclined blades; turbine type, for example Rushton turbine.
- the process according to the invention may further comprise at least one step of separating the organic solvent / product mixture formed from the aqueous solution, in particular by decantation.
- the aqueous phase is recovered separately during this separation step.
- this aqueous phase can be subjected to a novel treatment method according to the invention for the purpose of converting the fluorinated acid salts that have not yet been transformed (several extraction stages).
- the recovered aqueous phase may optionally be subjected to one or more liquid / liquid extractions with the abovementioned solvents without additional addition of reagents (several extraction stages).
- the process of the invention may further comprise at least one step of distillation of the organic solvent / product mixture formed from the separation step.
- This distillation step can be implemented by any method known to those skilled in the art.
- the size (especially the diameter) of the distillation columns depends on the circulating flow and the internal pressure. Their sizing will therefore be mainly according to the mixing rate to be treated.
- all the distillations used in the process of the invention are carried out at atmospheric pressure.
- the distillation column may be advantageously, but not exclusively, a column having the following specifications: number of theoretical stages: from 3 to 30, preferably from 3 to 25;
- separation columns comprising from 2 to 50 theoretical stages, preferably from 2 to 30 theoretical stages, in particular columns of the type: packed columns; stationary or moving trays; rotating disk columns; columns with agitated compartments, such as, for example, Kuhni columns; the pulsed columns, for example the pulsed columns with perforated discs; or batch reactors as described above placed in series with an overflow system continuously allowing the passage from one reactor to another.
- This distillation step may be preceded by a flash distillation step to obtain a concentrated organic medium formed product.
- This flash distillation step is preferably carried out at atmospheric pressure, in a distillation column comprising less than 10 theoretical stages, a flow rate R less than 5.
- the method according to the invention is preferably implemented in installations resistant to corrosion of the reaction medium. It is thus possible to use alloys based on molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon and tungsten sold under the trademarks HASTELLOY® or alloys of nickel, chromium, iron, manganese additives of copper and / or molybdenum sold under the name INCONEL® and more particularly alloys HASTELLOY C 276 or INCONEL 600, 625 or 718. It is also possible to choose stainless steels, such as austenitic steels [Robert H.
- a steel having a nickel content of at most 22% by weight is used, preferably between 6 and 20%, and more preferably between 8 and 14%.
- 316 and 316 L steels have a nickel content ranging from 10 to 14%.
- the material may also be selected from graphite materials and fluorinated polymers, and their derivatives. Of the fluoropolymers, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride) and PFA (perfluoroalkyl resins) are particularly suitable for carrying out the process of the invention. Finally, the material may be vitreous steel. The choice of material will depend on the reaction medium and salts it may contain, the skilled person is able to determine these materials with his general knowledge. Particularly preferred materials are vitreous steel and fluoropolymers.
- the organic solvent is chosen from solvents solubilizing the product formed but then allowing its separation for example by distillation.
- the organic solvent is chosen from solvents having a boiling point sufficiently far from the boiling point of the product formed to allow separation, in particular by distillation.
- the organic solvent used for the process of the invention may be a mixture of organic solvents.
- the organic solvent is chosen from apolar solvents.
- the organic solvent is chosen from aromatic solvents, halogenated aliphatic solvents, preferably chlorinated solvents, or alkyl ethers, preferably C 1 to C 15, preferably C 1 to C 10, alkyl ethers, or their mixtures.
- aromatic solvent denotes solvents having an aromatic ring, for example phenyl, optionally substituted with one or more groups, in particular chosen from linear or branched alkyl groups comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms. carbon atoms; halogen atoms, preferably chlorine; -Oalkyl groups with linear or branched alkyl comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms.
- the aromatic solvent is selected from xylene (ortho, meta or para), toluene, chlorobenzene, dichlorobenzene, mesithylene, methoxybenzene (anisole), 1,2-dimethoxybenzene (veratrole), ethylbenzene , trifluoromethylbenzene, or any of their mixtures.
- halogenated aliphatic is understood to mean a linear or branched alkyl chain comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and being substituted by one or more halogen atoms, especially chlorine.
- the organic solvent is selected from dichloromethane, dichloroethane, chloroform, or any of their mixtures.
- alkyl ether denotes linear or branched alkyl ethers, preferably comprising from 2 to 15 carbon atoms, for example from 2 to 10 carbon atoms.
- the alkyl ether is chosen from methyltertiobutyl ether (MTBE) or diisobutylether, or their mixture.
- the process of the invention may further comprise reacting the fluorinated acid salt with Brönsted acid and an alcohol to produce the corresponding ester.
- the products formed by the process of the invention are especially fluorinated acid or the ester of the fluorinated acid.
- the invention relates to a method of treating an aqueous solution comprising a fluorinated acid salt by reaction between said salt and a Brönsted acid in the presence of an organic solvent solubilizing the acid which is form, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution.
- the organic solvent is chosen from aromatic solvents, in particular substituted by one or more -Oalkyl groups with linear or branched alkyl comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; or the alkyl ethers.
- the solvent is methoxybenzene (anisole), 1,2-dimethoxybenzene (veratrole), MTBE or diisobutyl ether. This embodiment can advantageously be implemented from fluorinated acetic acid salt, and especially from DFA salt.
- the invention relates to a method of treating an aqueous solution comprising a fluorinated acid salt by reaction between said salt, a Brönsted acid and an alcohol in the presence of an organic solvent solubilizing the ester which is formed, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution.
- the fluorinated acid salt is as defined above. This embodiment is particularly well suited to the fluorinated aliphatic carboxylic acid salts as defined above and in particular to the salts of fluorinated acetic acids and more particularly to the salts of DFA.
- Such a process makes it possible surprisingly to obtain good conversion efficiencies of the fluorinated acid salt and good yields in terms of ester production of this acid.
- the process of the invention makes it possible to obtain a fluorinated acid ester of purity greater than 90%, preferably greater than 95%, more preferably close to 99%.
- the conversion efficiency of the fluorinated acid salt by the process of the invention is greater than 80% and preferably greater than 90%.
- the yield of fluorinated acid ester is greater than 80% and preferably greater than 90%.
- the process of the invention relates to a process for treating DFA salt and obtaining a DFA ester. All the variants and embodiments apply in particular to the DFA.
- the alcohol according to the invention is a water-soluble alcohol having a low molecular weight.
- the alcohol according to the invention is an alcohol of formula R 1 OH in which R 1 represents a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, pentyl and isopentyl.
- the alcohol is chosen from methanol, ethanol and isopropanol, the ester formed is then the ethyl, methyl or isopropyl ester of difluoroacetic acid.
- the alcohol is ethanol.
- the organic solvent is chosen from solvents solubilizing the ester formed but then allowing its separation by distillation.
- the organic solvent is chosen from solvents having a boiling point sufficiently far from the boiling point of the ester of the fluorinated acetic acid formed to allow a separation of the organic solvent and the ester, especially by distillation.
- the organic solvent is chosen from organic solvents having a boiling point of less than or equal to 90 ° C., preferably from 30 to 90 ° C. ° C or a boiling point greater than or equal to 100 ° C, preferably 100 to 200 ° C, for example from 1 to 180 ° C, measured at atmospheric pressure (101325 Pa).
- the organic solvent used for the reaction may be a mixture of solvents.
- the ester formed is the ethyl ester of fluorinated acetic acid and the organic solvent is chosen from the solvents solubilizing this ester.
- the organic solvent is chosen from apolar solvents.
- the different conditions described in the context of the process of the invention can be combined with each other.
- the solvent is chosen from aromatic solvents or chlorinated aliphatic solvents.
- the organic solvent may be chosen from aromatic solvents having a boiling point greater than or equal to 100 ° C., preferably from 100 to 200 ° C. for example from 1 to 180 ° C.
- the aromatic solvents defined above can be used.
- the organic solvent is selected from xylene (ortho, meta or para), toluene, chlorobenzene, dichlorobenzene, mesithylene, methoxybenzene (anisole), 1,2-dimethoxybenzene (veratrole), ethylbenzene , trifluoromethylbenzene, or any of their mixtures.
- the organic solvent may be chosen from halogenated aliphatic solvents having a boiling point less than or equal to 90 ° C., preferably from 30 to 90 ° C. vs.
- the halogenated aliphatics are in particular defined above.
- the organic solvent is selected from dichloromethane, dichloroethane, chloroform, or any of their mixtures.
- the organic solvent may be selected from C2 to C15, preferably C2 to C10, alkyl ethers.
- the process according to the invention may also comprise at least one step of separating the organic solvent / acid ester mixture formed from the aqueous solution, in particular by decantation. .
- the aqueous phase is recovered separately during this separation step.
- this aqueous phase can be subjected to a novel treatment method according to the invention for the purpose of converting the fluorinated acetic acid salts which have not yet been converted (several extraction stages).
- the recovered aqueous phase may optionally be subjected to one or more liquid / liquid extractions with the abovementioned solvents without additional addition of alcohol (several extraction stages).
- the process of the invention may further comprise at least one step of recovering the ester of the fluorinated acid by distillation of the organic solvent / acid ester mixture. fluorinated from the separation step.
- This distillation step can be implemented by any method known to those skilled in the art and in particular according to the variants and embodiments described above.
- the fraction whose boiling point is between 97 and 99 ° C. is recovered during this distillation, it corresponds to the fraction of the ester of the fluorinated acid having a purity greater than 90%, preferably greater than 95%, more preferably close to 99%.
- the organic solvent fraction obtained at the top of the column in the case of an organic solvent having a boiling point of less than 90 ° C., or obtained at the bottom of the column in the case of an organic solvent exhibiting a boiling temperature above 100 ° C, can be recycled to the esterification step of the process of the invention.
- the fractions containing the insufficiently pure fluorinated acid ester and the alcohol may be recycled to the esterification step of the process of the invention.
- This distillation step may be preceded by a flash distillation step to obtain a concentrated organic medium ester of fluorinated acetic acid.
- This flash distillation step is preferably carried out at atmospheric pressure, in a distillation column comprising less than 10 theoretical stages, a flow rate R less than 5.
- the invention relates to a process for preparing an ester from a fluorinated acid implementing the method of the invention.
- the present invention therefore also relates to a method for preparing a fluorinated acid ester comprising treating an aqueous solution comprising a salt of an organic compound comprising at least one acid function and at least one fluorine atom, said fluorinated acid, by reaction between said salt, an alcohol and at least one Brönsted acid in the presence of an organic solvent solubilizing the product that is formed, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution.
- the embodiments and preferred modes described above also apply to the process for preparing the fluorinated acid ester.
- the temperature is expressed in degrees Celsius and is the ambient temperature (20-25 ° C) unless stated otherwise.
- the pressure is atmospheric unless otherwise indicated.
- Rushton is added 574.7 g of an aqueous solution containing 14.4% by weight of sodium difluoroacetate and 9% by weight of sodium chloride as well as 126 g of concentrated sulfuric acid at 98% by weight. Sulfuric acid is added in 1 hour so as to keep the temperature below 50 ° C. After returning to ambient temperature, 207 g of xylene (o-, m-, p- isomer mixture) and 39.7 g of ethanol are added. The medium is stirred at 850 rpm for one hour at room temperature. The stirring is then stopped and the upper organic phase is recovered by decantation. Two additional liquid liquid extraction operations are carried out from the aqueous solution obtained, with the addition of twice 207 g of xylenes.
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Abstract
The present invention relates to a method for processing an aqueous solution containing a salt of an organic compound including at least one acid function and at least one fluorine atom, or fluoric acid, by reaction between said salt and at least one Bronsted acid and an alcohol in the presence of an organic solvent solubilizing the resulting product, wherein said organic solvent consists of at least one dual-phase liquid/liquid reaction medium with the aqueous solution.
Description
Procédé de traitement d'acide fluoré Fluoric acid treatment process
La présente invention concerne un procédé de traitement d'acide fluoré, notamment d'acide acétique fluoré, par exemple de l'acide difluoroacétique (DFA) ou de l'acide trifluoroacétique (TFA), notamment un procédé de traitement d'acide fluoré sous forme salifiée dans une solution aqueuse. The present invention relates to a process for the treatment of fluorinated acid, in particular of fluorinated acetic acid, for example difluoroacetic acid (DFA) or trifluoroacetic acid (TFA), in particular a process for the treatment of fluorinated acid under salified form in an aqueous solution.
Le DFA peut être produit par différents procédés et selon le procédé peut se trouver solubilisé dans une solution aqueuse sous la forme d'un sel, notamment de sodium. Le DFA, même après acidification, est soluble en solution aqueuse ; ceci rend par conséquent sa récupération, par exemple par distillation ou extraction, très difficile. DFA can be produced by different processes and according to the process can be solubilized in an aqueous solution in the form of a salt, especially sodium salt. DFA, even after acidification, is soluble in aqueous solution; this makes its recovery, for example by distillation or extraction, very difficult.
Il y a donc un besoin de fournir un procédé permettant de traiter les acides fluorés solubles en phase aqueuse et en particulier le DFA ou le TFA, notamment lorsqu'ils sont sous forme de sels dans une solution aqueuse. There is therefore a need to provide a process for treating soluble fluorinated acids in the aqueous phase and in particular DFA or TFA, especially when they are in the form of salts in an aqueous solution.
L'objectif de la présente invention est de fournir un procédé de traitement d'acide fluoré, notamment un procédé de traitement d'un sel d'acide fluoré en solution aqueuse, en particulier du DFA ou du TFA. The object of the present invention is to provide a process for the treatment of fluorinated acid, in particular a process for treating a fluorinated acid salt in aqueous solution, in particular DFA or TFA.
Un autre objectif de la présente invention est de fournir un tel procédé qui soit de mise en œuvre simple et qui permette d'obtenir un produit valorisable dans de bons rendements et avec une pureté élevée. Another object of the present invention is to provide such a method which is simple to implement and which makes it possible to obtain a product that can be recovered in good yields and with high purity.
Le procédé de la présente invention permet de remédier aux différents problèmes précités. The method of the present invention makes it possible to remedy the various problems mentioned above.
Les inventeurs ont découvert de manière surprenante qu'il était possible de traiter une solution aqueuse contenant un sel d'acide fluoré soluble en phase aqueuse, par estérification de ce sel en milieu acide. The inventors have surprisingly discovered that it is possible to treat an aqueous solution containing a fluorinated acid salt soluble in aqueous phase, by esterification of this salt in acidic medium.
Cependant, si l'on effectue l'estérification du sel d'acide fluoré, notamment de DFA ou de TFA, directement dans la solution aqueuse par ajout d'un acide et de l'alcool souhaité, dès sa formation, l'ester, qui est un ester d'acide fort, s'hydrolyse. Il n'est donc pas possible par cette méthode de récupérer un ester d'acide fluoré, notamment de DFA ou de TFA, avec de bons rendements. However, if the esterification of the fluorinated acid salt, in particular DFA or TFA, is carried out directly in the aqueous solution by adding an acid and the desired alcohol, as soon as it is formed, the ester, which is a strong acid ester, hydrolyzes. It is therefore not possible by this method to recover a fluorinated acid ester, especially DFA or TFA, with good yields.
Le procédé de l'invention permet de résoudre également ce problème technique. La présente invention concerne un procédé de traitement d'une solution aqueuse comprenant un sel d'un composé organique comprenant au moins une fonction acide et
au moins un atome de fluor, dit acide fluoré par réaction entre ledit sel et au moins un acide de Brônsted en présence d'un solvant organique solubilisant le produit qui se forme, ledit solvant organique formant au moins un milieu réactionnel biphasique liquide/liquide avec la solution aqueuse. Dans le cadre de l'invention, l'acide fluoré est notamment choisi parmi les acides carboxyliques fluorés solubles dans l'eau. De préférence, l'acide est choisi parmi les acides carboxyliques, aliphatiques comprenant au moins un atome de fluor et comprenant de 2 à 15 atomes de carbone, de préférence de 2 à 10 atomes de carbone. On peut citer, à titre d'exemple préférentiel, les acides acétiques fluorés. The method of the invention also solves this technical problem. The present invention relates to a method for treating an aqueous solution comprising a salt of an organic compound comprising at least one acid function and at least one fluorine atom, said fluoro acid, by reaction between said salt and at least one Brönsted acid in the presence of an organic solvent solubilizing the product that is formed, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution. In the context of the invention, the fluorinated acid is especially chosen from fluorinated carboxylic acids soluble in water. Preferably, the acid is chosen from aliphatic carboxylic acids comprising at least one fluorine atom and comprising from 2 to 15 carbon atoms, preferably from 2 to 10 carbon atoms. As a preferred example, mention may be made of fluorinated acetic acids.
Dans le cadre de la présente invention on entend par le terme « acide acétique fluoré» désigner les acides mono-, di- et trifluoroacétiques, et l'un quelconque de leurs mélanges, de préférence les acides di- et trifluoroacétiques, plus particulièrement l'acide difluoroacétique. In the context of the present invention, the term "fluoroacetic acid" is intended to denote mono-, di- and trifluoroacetic acids, and any of their mixtures, preferably di- and trifluoroacetic acids, more particularly the difluoroacetic acid.
Dans un mode de réalisation particulier, la solution aqueuse comprenant le sel d'acide fluoré est une solution aqueuse provenant d'un procédé de préparation dudit acide. In a particular embodiment, the aqueous solution comprising the fluorinated acid salt is an aqueous solution from a process for preparing said acid.
Dans un autre mode de réalisation, la solution aqueuse comprenant le sel d'acide fluoré est un effluent, l'acide fluoré étant alors un sous-produit à valoriser. In another embodiment, the aqueous solution comprising the fluorinated acid salt is an effluent, the fluorinated acid then being a by-product to be upgraded.
Comme indiqué précédemment, l'acide fluoré se trouve sous forme salifiée dans la solution aqueuse, le contre-ion peut notamment être choisi parmi les éléments des colonnes 1 à 12 de la classification périodique des éléments, de préférence le contre-ion est un alcalin ou un alcalino-terreux, par exemple le sodium, le potassium ou le lithium. As indicated above, the fluorinated acid is in salified form in the aqueous solution, the counterion may in particular be chosen from the elements of columns 1 to 12 of the periodic table of the elements, preferably the counterion is an alkaline or an alkaline earth metal, for example sodium, potassium or lithium.
La solution aqueuse de sel de l'acide fluoré peut également comprendre un ou plusieurs sels inorganiques, notamment de formule MX dans laquelle X est un atome d'halogène, notamment fluor ou chlore, et M est un élément choisi parmi les éléments des colonnes 1 à 12 du tableau périodique des éléments, de préférence M est un alcalin ou un alcalino-terreux, par exemple le sodium, le potassium ou le lithium. Ces sels peuvent être compris dans la solution aqueuse à raison de 5 à 80% en poids par rapport au poids total de la solution aqueuse comprenant le sel de l'acide fluoré. La présence de ces sels inorganiques en plus du sel de l'acide fluoré a pour conséquence une augmentation de la densité de la phase aqueuse. Le choix du solvant organique parmi les solvants précités s'effectue alors en fonction de la densité du milieu aqueux comprenant le sel de l'acide fluoré salifié.
On entend par « au moins un milieu réactionnel biphasique liquide/liquide » désigner un milieu comprenant deux phases liquides d'une part la phase solvant organique et d'autre part la phase aqueuse, un tel milieu pouvant en outre comprendre des composés solides en suspension tels que par exemple des sels précipités. The aqueous solution of the salt of the fluorinated acid may also comprise one or more inorganic salts, especially of formula MX in which X is a halogen atom, in particular fluorine or chlorine, and M is a member chosen from the elements of the columns 1 to 12 of the periodic table of elements, preferably M is an alkali or an alkaline earth, for example sodium, potassium or lithium. These salts may be included in the aqueous solution in a proportion of 5 to 80% by weight relative to the total weight of the aqueous solution comprising the salt of the fluorinated acid. The presence of these inorganic salts in addition to the salt of the fluorinated acid results in an increase in the density of the aqueous phase. The choice of the organic solvent among the abovementioned solvents is then carried out as a function of the density of the aqueous medium comprising the salt of the salified fluorinated acid. The term "at least one biphasic liquid / liquid reaction medium" denotes a medium comprising two liquid phases, on the one hand the organic solvent phase and, on the other hand, the aqueous phase, such a medium may also comprise suspended solid compounds. such as, for example, precipitated salts.
On entend par « acide de Brônsted » une molécule capable de céder un ou plusieurs protons. The term "Brönsted acid" means a molecule capable of yielding one or more protons.
De préférence, un acide de Brônsted selon l'invention est choisi parmi les acides forts dont le pKa est inférieur à 2, et en particulier parmi HCI, H2S04, HN03, HBr ou H3P04, pur ou dilué, ou l'un quelconques de leurs mélanges. L'acide chlorhydrique peut être utilisé sous forme gazeuse et/ou en solution (solution aqueuse). De façon préférée, l'acide est utilisé dans des proportions de 1 à 5 équivalents molaires, de préférence de 1 à 3 équivalents molaires, par rapport au sel de l'acide fluoré. Preferably, a Brönsted acid according to the invention is chosen from strong acids whose pKa is less than 2, and in particular from HCl, H 2 SO 4 , HNO 3 , HBr or H 3 PO 4 , pure or diluted, or any of their mixtures. Hydrochloric acid can be used in gaseous form and / or in solution (aqueous solution). Preferably, the acid is used in proportions of 1 to 5 molar equivalents, preferably 1 to 3 molar equivalents, relative to the salt of the fluorinated acid.
La réaction du sel d'acide fluoré avec l'acide de Brônsted permet l'obtention de l'acide fluoré correspondant. The reaction of the fluorinated acid salt with Brönsted acid makes it possible to obtain the corresponding fluorinated acid.
Avantageusement, le produit formé à partir de la réaction entre le sel d'acide fluoré et l'acide de Brônsted est solubilisé par le solvant organique. Advantageously, the product formed from the reaction between the fluorinated acid salt and the Brönsted acid is solubilized by the organic solvent.
Le solvant organique est de préférence un solvant immiscible dans l'eau permettant ainsi de former un milieu réactionnel au moins biphasique liquide/liquide avant et après réaction du sel d'acide fluoré avec au moins un acide de Brônsted. The organic solvent is preferably a solvent immiscible in water, thus making it possible to form a liquid / liquid at least two-phase reaction medium before and after reacting the fluorinated acid salt with at least one Brönsted acid.
Bien que le solvant organique puisse être utilisé en toute proportion ; il est de préférence utilisé dans des proportions de 50 à 200%, de préférence de 50 à 100%, en volume par rapport au volume de la solution aqueuse. Le procédé de l'invention peut être mis en œuvre à une température de 10 àAlthough the organic solvent can be used in any proportion; it is preferably used in proportions of 50 to 200%, preferably 50 to 100% by volume relative to the volume of the aqueous solution. The process of the invention can be carried out at a temperature of 10 to
100°C, de préférence de 20 à 80°C. 100 ° C, preferably from 20 to 80 ° C.
Dans un mode de réalisation particulier, le procédé de l'invention est mis en œuvre en batch.
Dans un autre mode de réalisation particulier, le procédé de l'invention est mis en œuvre en continu. In a particular embodiment, the method of the invention is implemented in batch. In another particular embodiment, the method of the invention is implemented continuously.
De préférence, le procédé de l'invention, est réalisé en mettant en contact intime les différentes phases du milieu réactionnel. Il convient alors de disperser de manière fine l'une des phases dans l'autre afin d'augmenter la surface de contact et par conséquent la cinétique de la réaction. Cela peut être fait par toute méthode connue de l'homme du métier. Preferably, the process of the invention is carried out by bringing into intimate contact the different phases of the reaction medium. It is then necessary to disperse finely one of the phases in the other in order to increase the contact surface and therefore the kinetics of the reaction. This can be done by any method known to those skilled in the art.
Dans le cadre d'un procédé mis en œuvre en batch il est préférable d'utiliser un réacteur pourvu d'un système d'agitation permettant une forte agitation du milieu réactionnel, notamment un réacteur pourvu d'un système d'agitation de type 4 pales, notamment 4 pales inclinées ; de type turbine, par exemple turbine Rushton. In the context of a process carried out in batch mode, it is preferable to use a reactor provided with a stirring system that allows a strong stirring of the reaction medium, in particular a reactor equipped with a type 4 stirring system. blades, in particular four inclined blades; turbine type, for example Rushton turbine.
Le procédé selon l'invention peut comprendre en outre au moins une étape de séparation du mélange solvant organique/produit formé de la solution aqueuse, notamment par décantation. The process according to the invention may further comprise at least one step of separating the organic solvent / product mixture formed from the aqueous solution, in particular by decantation.
La phase aqueuse est récupérée séparément lors de cette étape de séparation. Dans un mode de réalisation, on peut soumettre cette phase aqueuse à un nouveau procédé de traitement selon l'invention dans le but de transformer les sels d'acide fluoré qui n'auraient pas encore été transformés (plusieurs étages d'extraction). The aqueous phase is recovered separately during this separation step. In one embodiment, this aqueous phase can be subjected to a novel treatment method according to the invention for the purpose of converting the fluorinated acid salts that have not yet been transformed (several extraction stages).
Dans un autre mode de réalisation, la phase aqueuse récupérée peut éventuellement être soumise à une ou plusieurs extractions liquide/liquide avec les solvants précités sans ajout supplémentaire de réactifs (plusieurs étages d'extraction). In another embodiment, the recovered aqueous phase may optionally be subjected to one or more liquid / liquid extractions with the abovementioned solvents without additional addition of reagents (several extraction stages).
Afin de récupérer le produit formé, le procédé de l'invention peut comprendre en outre au moins une étape de distillation du mélange solvant organique/produit formé issu de l'étape de séparation. In order to recover the product formed, the process of the invention may further comprise at least one step of distillation of the organic solvent / product mixture formed from the separation step.
Cette étape de distillation peut être mise en œuvre par toute méthode connue de l'homme du métier. La taille (notamment le diamètre) des colonnes de distillation dépend du flux circulant et de la pression interne. Leur dimensionnement se fera donc principalement suivant le débit de mélange à traiter. De préférence, l'ensemble des distillations mises en œuvre dans le procédé de l'invention sont effectuées à pression atmosphérique. This distillation step can be implemented by any method known to those skilled in the art. The size (especially the diameter) of the distillation columns depends on the circulating flow and the internal pressure. Their sizing will therefore be mainly according to the mixing rate to be treated. Preferably, all the distillations used in the process of the invention are carried out at atmospheric pressure.
De préférence, pour cette étape de distillation, la colonne de distillation pourra être avantageusement, mais non limitativement, une colonne ayant les spécifications suivantes :
nombre d'étages théoriques : de 3 à 30, de préférence de 3 à 25 ; Preferably, for this distillation step, the distillation column may be advantageously, but not exclusively, a column having the following specifications: number of theoretical stages: from 3 to 30, preferably from 3 to 25;
- taux de reflux R : de 2 à 10. reflux ratio R: from 2 to 10.
Dans le cadre d'un procédé mis en œuvre en continu il est préférable d'utiliser des colonnes de séparation comprenant de 2 à 50 étages théoriques, de préférence de 2 à 30 étages théoriques, notamment des colonnes de type : colonnes à garnissage ; colonnes à plateaux fixes ou mobiles ; colonnes à disques rotatifs ; colonnes à compartiments agités, tel que par exemple les colonnes Kuhni ; les colonnes puisées, par exemple les colonnes puisées à disques perforés ; ou des réacteurs batch tels que décrits ci-dessus mis en série avec un système de débordement permettant de façon continue le passage d'un réacteur à un autre. In the context of a method implemented continuously, it is preferable to use separation columns comprising from 2 to 50 theoretical stages, preferably from 2 to 30 theoretical stages, in particular columns of the type: packed columns; stationary or moving trays; rotating disk columns; columns with agitated compartments, such as, for example, Kuhni columns; the pulsed columns, for example the pulsed columns with perforated discs; or batch reactors as described above placed in series with an overflow system continuously allowing the passage from one reactor to another.
Cette étape de distillation peut être précédée d'une étape de flash distillation permettant d'obtenir un milieu organique concentré en produit formé. Cette étape de distillation flash est de préférence mise en œuvre à pression atmosphérique, dans une colonne de distillation comprenant moins de 10 étages théoriques, un taux de flux R inférieur à 5. This distillation step may be preceded by a flash distillation step to obtain a concentrated organic medium formed product. This flash distillation step is preferably carried out at atmospheric pressure, in a distillation column comprising less than 10 theoretical stages, a flow rate R less than 5.
Le procédé selon l'invention est de préférence mis en œuvre dans des installations résistantes à la corrosion du milieu réactionnel. Il est ainsi possible d'utiliser des alliages à base de molybdène, chrome, cobalt, fer, cuivre, manganèse, titane, zirconium, aluminium, carbone et tungstène vendus sous les marques HASTELLOY® ou les alliages de nickel, chrome, fer, manganèse additivés de cuivre et/ou molybdène commercialisés sous la dénomination INCONEL® et plus particulièrement les alliages HASTELLOY C 276 ou INCONEL 600, 625 ou 718. On peut choisir également les aciers inoxydables, tels que les aciers austénitiques [Robert H. Perry et al, Perry's Chemical Engineers' Handbook, Sixth Edition (1984), page 23-44], et plus particulièrement les aciers inoxydables 316 ou 316 L. On met en œuvre un acier ayant une teneur en nickel au plus de 22 % en masse, de préférence comprise entre 6 et 20 %, et plus préférentiellement comprise entre 8 et 14 %. Les aciers 316 et 316 L ont une teneur en nickel variant entre 10 et 14 %. Le matériau peut également être choisi parmi les matériaux graphites et les polymères fluorés, et leurs dérivés. Parmi les polymères fluorés, le PTFE (polytétrafluoroéthylène), le PVDF (polyfluorure de vinylidène) et le PFA (résines perfluoroalkyles) sont particulièrement adaptés pour la mise en œuvre du procédé de l'invention. Enfin, le matériau peut être de l'acier vitrifié.
Le choix du matériau va dépendre du milieu réactionnel et des sels qu'il peut contenir, l'homme du métier est à même de déterminer ces matériaux avec ses connaissances générales. Les matériaux particulièrement préférés sont l'acier vitrifié et les polymères fluorés. The method according to the invention is preferably implemented in installations resistant to corrosion of the reaction medium. It is thus possible to use alloys based on molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon and tungsten sold under the trademarks HASTELLOY® or alloys of nickel, chromium, iron, manganese additives of copper and / or molybdenum sold under the name INCONEL® and more particularly alloys HASTELLOY C 276 or INCONEL 600, 625 or 718. It is also possible to choose stainless steels, such as austenitic steels [Robert H. Perry et al, Perry's Chemical Engineers' Handbook, Sixth Edition (1984), page 23-44], and more particularly stainless steels 316 or 316 L. A steel having a nickel content of at most 22% by weight is used, preferably between 6 and 20%, and more preferably between 8 and 14%. 316 and 316 L steels have a nickel content ranging from 10 to 14%. The material may also be selected from graphite materials and fluorinated polymers, and their derivatives. Of the fluoropolymers, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride) and PFA (perfluoroalkyl resins) are particularly suitable for carrying out the process of the invention. Finally, the material may be vitreous steel. The choice of material will depend on the reaction medium and salts it may contain, the skilled person is able to determine these materials with his general knowledge. Particularly preferred materials are vitreous steel and fluoropolymers.
Le solvant organique est choisi parmi les solvants solubilisant le produit formé mais permettant ensuite sa séparation par exemple par distillation. Ainsi, et de façon préférée, le solvant organique est choisi parmi les solvants présentant une température d'ébullition suffisamment éloignée de la température d'ébullition du produit formé pour permettre une séparation, notamment par distillation. Le solvant organique utilisé pour le procédé de l'invention peut être un mélange de solvants organiques. The organic solvent is chosen from solvents solubilizing the product formed but then allowing its separation for example by distillation. Thus, and preferably, the organic solvent is chosen from solvents having a boiling point sufficiently far from the boiling point of the product formed to allow separation, in particular by distillation. The organic solvent used for the process of the invention may be a mixture of organic solvents.
De façon avantageuse, le solvant organique est choisi parmi les solvants apolaires. De préférence, le solvant organique est choisi parmi les solvants aromatiques, les solvants aliphatiques halogénés, de préférence chlorés, ou les éthers d'alkyle, de préférence les éthers d'alkyle en C1 à C15, de préférence en C1 à C10, ou leurs mélanges. Advantageously, the organic solvent is chosen from apolar solvents. Preferably, the organic solvent is chosen from aromatic solvents, halogenated aliphatic solvents, preferably chlorinated solvents, or alkyl ethers, preferably C 1 to C 15, preferably C 1 to C 10, alkyl ethers, or their mixtures.
On entend par solvant aromatique désigner les solvants présentant un cycle aromatique, par exemple phényle, éventuellement substitué par un ou plusieurs groupes, notamment choisis parmi les groupes alkyles, linéaires ou ramifiés comprenant de 1 à 10 atomes de carbone, de préférence de 1 à 5 atomes de carbone ; les atomes d'halogène, de préférence le chlore ; les groupes -Oalkyle avec alkyle linéaire ou ramifié comprenant de 1 à 10 atomes de carbone, de préférence de 1 à 5 atomes de carbone. De préférence, le solvant aromatique est choisi parmi le xylène (ortho, meta ou para), le toluène, le chlorobenzène, le dichlorobenzène, le mésithylène, le méthoxybenzène (anisole), le 1 ,2- diméthoxybenzène (vératrole), l'éthylbenzène, le trifluorométhylbenzène, ou l'un quelconque de leurs mélanges. The term "aromatic solvent" denotes solvents having an aromatic ring, for example phenyl, optionally substituted with one or more groups, in particular chosen from linear or branched alkyl groups comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms. carbon atoms; halogen atoms, preferably chlorine; -Oalkyl groups with linear or branched alkyl comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms. Preferably, the aromatic solvent is selected from xylene (ortho, meta or para), toluene, chlorobenzene, dichlorobenzene, mesithylene, methoxybenzene (anisole), 1,2-dimethoxybenzene (veratrole), ethylbenzene , trifluoromethylbenzene, or any of their mixtures.
On entend par aliphatique halogéné une chaîne alkyle, linéaire ou ramifié, comprenant de 1 à 10 atomes de carbone, de préférence de 1 à 5 atomes de carbone, et étant substitué par un ou plusieurs atomes d'halogène, notamment le chlore. De préférence, le solvant organique est choisi parmi le dichlorométhane, le dichloroéthane, le chloroforme, ou l'un quelconque de leurs mélanges. The term "halogenated aliphatic" is understood to mean a linear or branched alkyl chain comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and being substituted by one or more halogen atoms, especially chlorine. Preferably, the organic solvent is selected from dichloromethane, dichloroethane, chloroform, or any of their mixtures.
On entend par éther d'alkyle désigner des éthers d'alkyle linéaire ou ramifié, comprenant de préférence de 2 à 15 atomes de carbone, par exemple de 2 à 10 atomes de carbone. De préférence, l'éther d'alkyle est choisi parmi le méthyltertiobutyl éther (MTBE) ou le diisobutyléther, ou leur mélange.
Le procédé de l'invention peut en outre comprendre la réaction du sel d'acide fluoré avec l'acide de Brônsted et un alcool pour produire l'ester correspondant. The term "alkyl ether" denotes linear or branched alkyl ethers, preferably comprising from 2 to 15 carbon atoms, for example from 2 to 10 carbon atoms. Preferably, the alkyl ether is chosen from methyltertiobutyl ether (MTBE) or diisobutylether, or their mixture. The process of the invention may further comprise reacting the fluorinated acid salt with Brönsted acid and an alcohol to produce the corresponding ester.
Ainsi, les produits formés par le procédé de l'invention sont notamment l'acide fluoré ou l'ester de l'acide fluoré. Thus, the products formed by the process of the invention are especially fluorinated acid or the ester of the fluorinated acid.
Dans un mode de réalisation particulier, l'invention concerne un procédé de traitement d'une solution aqueuse comprenant un sel d'acide fluoré par réaction entre ledit sel et un acide de Brônsted en présence d'un solvant organique solubilisant l'acide qui se forme, ledit solvant organique formant au moins un milieu réactionnel biphasique liquide/liquide avec la solution aqueuse. In a particular embodiment, the invention relates to a method of treating an aqueous solution comprising a fluorinated acid salt by reaction between said salt and a Brönsted acid in the presence of an organic solvent solubilizing the acid which is form, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution.
Le sel d'acide fluoré, l'acide de Brônsted et le solvant organique étant tels que définis plus haut. De préférence, le solvant organique est choisi parmi les solvants aromatiques, notamment substitués par un ou plusieurs groupes -Oalkyle avec alkyle linéaire ou ramifié comprenant de 1 à 10 atomes de carbone, de préférence de 1 à 5 atomes de carbone ; ou les éthers d'alkyle. De préférence, le solvant est le méthoxybenzène (anisole), le 1 ,2-diméthoxybenzène (vératrole), le MTBE ou le diisobutyléther. Ce mode de réalisation peut de façon avantageuse être mis en œuvre à partir de sel d'acide acétique fluoré, et notamment à partir de sel de DFA. The fluorinated acid salt, Brönsted acid and the organic solvent being as defined above. Preferably, the organic solvent is chosen from aromatic solvents, in particular substituted by one or more -Oalkyl groups with linear or branched alkyl comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; or the alkyl ethers. Preferably, the solvent is methoxybenzene (anisole), 1,2-dimethoxybenzene (veratrole), MTBE or diisobutyl ether. This embodiment can advantageously be implemented from fluorinated acetic acid salt, and especially from DFA salt.
Dans un mode de réalisation particulièrement préféré, l'invention concerne un procédé de traitement d'une solution aqueuse comprenant un sel d'acide fluoré par réaction entre ledit sel, un acide de Brônsted et un alcool en présence d'un solvant organique solubilisant l'ester qui se forme, ledit solvant organique formant au moins un milieu réactionnel biphasique liquide/liquide avec la solution aqueuse. In a particularly preferred embodiment, the invention relates to a method of treating an aqueous solution comprising a fluorinated acid salt by reaction between said salt, a Brönsted acid and an alcohol in the presence of an organic solvent solubilizing the ester which is formed, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution.
Le sel d'acide fluoré est tel que défini plus haut. Ce mode de réalisation est particulièrement bien adapté aux sels d'acides carboxyliques aliphatiques fluorés tels que définis ci-dessus et notamment aux sels d'acides acétiques fluorés et plus particulièrement aux sels de DFA. The fluorinated acid salt is as defined above. This embodiment is particularly well suited to the fluorinated aliphatic carboxylic acid salts as defined above and in particular to the salts of fluorinated acetic acids and more particularly to the salts of DFA.
Un tel procédé permet d'obtenir de manière surprenante de bons rendements de conversion du sel d'acide fluoré et de bons rendements en termes de production d'ester de cet acide. Le procédé de l'invention permet d'obtenir un ester d'acide fluoré de pureté
supérieure à 90%, de préférence supérieure à 95%, de manière plus préférée proche de 99%. Par ailleurs, le rendement de conversion du sel d'acide fluoré par le procédé de l'invention est supérieur à 80 % et de préférence supérieure à 90 %. Le rendement en ester d'acide fluoré est supérieur à 80 % et de préférence supérieur à 90%. Such a process makes it possible surprisingly to obtain good conversion efficiencies of the fluorinated acid salt and good yields in terms of ester production of this acid. The process of the invention makes it possible to obtain a fluorinated acid ester of purity greater than 90%, preferably greater than 95%, more preferably close to 99%. Furthermore, the conversion efficiency of the fluorinated acid salt by the process of the invention is greater than 80% and preferably greater than 90%. The yield of fluorinated acid ester is greater than 80% and preferably greater than 90%.
Dans un mode de réalisation particulier, le procédé de l'invention concerne un procédé de traitement de sel de DFA et l'obtention d'un ester de DFA. L'ensemble des variantes et des modes de réalisation s'applique en particulier au DFA. De préférence, l'alcool selon l'invention est un alcool soluble dans l'eau, présentant une faible masse moléculaire. De préférence, l'alcool selon l'invention est un alcool de formule R1OH dans laquelle R1 représente un groupe alkyle, linéaire ou ramifié, comprenant de 1 à 10 atomes de carbone, de préférence de 1 à 5 atomes de carbone, par exemple méthyle, éthyle, propyle, isopropyle, butyle, pentyle et isopentyle. De préférence l'alcool est choisi parmi le méthanol, l'éthanol et l'isopropanol, l'ester formé est alors l'ester éthylique, méthylique ou isopropilique de l'acide difluoroacétique. De manière particulièrement préférée, l'alcool est l'éthanol. In a particular embodiment, the process of the invention relates to a process for treating DFA salt and obtaining a DFA ester. All the variants and embodiments apply in particular to the DFA. Preferably, the alcohol according to the invention is a water-soluble alcohol having a low molecular weight. Preferably, the alcohol according to the invention is an alcohol of formula R 1 OH in which R 1 represents a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, pentyl and isopentyl. Preferably, the alcohol is chosen from methanol, ethanol and isopropanol, the ester formed is then the ethyl, methyl or isopropyl ester of difluoroacetic acid. In a particularly preferred manner, the alcohol is ethanol.
Il est préférable que les quantités d'alcool soient maîtrisées. De préférence, l'alcool est utilisé dans des proportions de 1 à 5 équivalents molaires par rapport au sel de l'acide acétique fluoré de préférence de 1 à 4 équivalents molaires. It is preferable that the quantities of alcohol are controlled. Preferably, the alcohol is used in proportions of 1 to 5 molar equivalents with respect to the salt of fluorinated acetic acid, preferably of 1 to 4 molar equivalents.
De préférence, le solvant organique est choisi parmi les solvants solubilisant l'ester formé mais permettant ensuite sa séparation par distillation. Ainsi et de façon préférée, le solvant organique est choisi parmi les solvants présentant une température d'ébullition suffisamment éloignée de la température d'ébullition de l'ester de l'acide acétique fluoré formé pour permettre une séparation du solvant organique et de l'ester, notamment par distillation. Ainsi, et de façon préférée, en particulier dans le cas où l'alcool est l'éthanol, le solvant organique est choisi parmi les solvants organique présentant une température d'ébullition inférieure ou égale à 90°C, de préférence de 30 à 90°C ou une température d'ébullition supérieure ou égale à 100°C, de préférence de 100 à 200°C, par exemple de 1 10 à 180°C, mesurée à pression atmosphérique (101325 Pa). Preferably, the organic solvent is chosen from solvents solubilizing the ester formed but then allowing its separation by distillation. Thus, and preferably, the organic solvent is chosen from solvents having a boiling point sufficiently far from the boiling point of the ester of the fluorinated acetic acid formed to allow a separation of the organic solvent and the ester, especially by distillation. Thus, and preferably, especially in the case where the alcohol is ethanol, the organic solvent is chosen from organic solvents having a boiling point of less than or equal to 90 ° C., preferably from 30 to 90 ° C. ° C or a boiling point greater than or equal to 100 ° C, preferably 100 to 200 ° C, for example from 1 to 180 ° C, measured at atmospheric pressure (101325 Pa).
Le solvant organique utilisé pour la réaction peut être un mélange de solvants. Selon une variante préférée l'ester formé est l'ester éthylique de l'acide acétique fluoré et le solvant organique est choisi parmi les solvants solubilisant cet ester. The organic solvent used for the reaction may be a mixture of solvents. According to a preferred variant, the ester formed is the ethyl ester of fluorinated acetic acid and the organic solvent is chosen from the solvents solubilizing this ester.
De façon avantageuse, le solvant organique est choisi parmi les solvants apolaires.
Les différentes conditions décrites dans le cadre du procédé de l'invention peuvent être combinées entre elles. Advantageously, the organic solvent is chosen from apolar solvents. The different conditions described in the context of the process of the invention can be combined with each other.
De préférence, le solvant est choisi parmi les solvants aromatiques ou les solvants aliphatiques chlorés. Preferably, the solvent is chosen from aromatic solvents or chlorinated aliphatic solvents.
Dans un mode de réalisation particulier, en particulier lorsque l'alcool est l'éthanol, le solvant organique peut être choisi parmi les solvants aromatiques ayant une température d'ébullition supérieure ou égale à 100°C, de préférence de 100 à 200°C, par exemple de 1 10 à 180°C. Les solvants aromatiques définis plus haut peuvent être utilisés. De préférence, le solvant organique est choisi parmi le xylène (ortho, meta ou para), le toluène, le chlorobenzène, le dichlorobenzène, le mésithylène, le méthoxybenzène (anisole), le 1 ,2-diméthoxybenzène (vératrole), l'éthylbenzène, le trifluorométhylbenzène, ou l'un quelconque de leurs mélanges. In a particular embodiment, in particular when the alcohol is ethanol, the organic solvent may be chosen from aromatic solvents having a boiling point greater than or equal to 100 ° C., preferably from 100 to 200 ° C. for example from 1 to 180 ° C. The aromatic solvents defined above can be used. Preferably, the organic solvent is selected from xylene (ortho, meta or para), toluene, chlorobenzene, dichlorobenzene, mesithylene, methoxybenzene (anisole), 1,2-dimethoxybenzene (veratrole), ethylbenzene , trifluoromethylbenzene, or any of their mixtures.
Dans un autre mode de réalisation, en particulier lorsque l'alcool est l'éthanol, le solvant organique peut être choisi parmi les solvants aliphatiques halogénés ayant une température d'ébullition inférieure ou égale à 90°C, de préférence de 30 à 90°C. Les aliphatiques halogénés sont notamment définis plus haut. De préférence, le solvant organique est choisi parmi le dichlorométhane, le dichloroéthane, le chloroforme, ou l'un quelconque de leurs mélanges. In another embodiment, particularly when the alcohol is ethanol, the organic solvent may be chosen from halogenated aliphatic solvents having a boiling point less than or equal to 90 ° C., preferably from 30 to 90 ° C. vs. The halogenated aliphatics are in particular defined above. Preferably, the organic solvent is selected from dichloromethane, dichloroethane, chloroform, or any of their mixtures.
Dans un autre mode de réalisation, en particulier lorsque l'alcool est l'éthanol, le solvant organique peut être choisi parmi les éthers d'alkyle en C2 à C15, de préférence en C2 à C10. Dans le mode de réalisation dans lequel le procédé met en œuvre un alcool, le procédé selon l'invention peut comprendre en outre au moins une étape de séparation du mélange solvant organique/ester de l'acide formé de la solution aqueuse, notamment par décantation. In another embodiment, particularly when the alcohol is ethanol, the organic solvent may be selected from C2 to C15, preferably C2 to C10, alkyl ethers. In the embodiment in which the process uses an alcohol, the process according to the invention may also comprise at least one step of separating the organic solvent / acid ester mixture formed from the aqueous solution, in particular by decantation. .
La phase aqueuse est récupérée séparément lors de cette étape de séparation. Dans un mode de réalisation, on peut soumettre cette phase aqueuse à un nouveau procédé de traitement selon l'invention dans le but de transformer les sels d'acide acétique fluoré qui n'auraient pas encore été transformés (plusieurs étages d'extraction). The aqueous phase is recovered separately during this separation step. In one embodiment, this aqueous phase can be subjected to a novel treatment method according to the invention for the purpose of converting the fluorinated acetic acid salts which have not yet been converted (several extraction stages).
Dans un autre mode de réalisation, la phase aqueuse récupérée peut éventuellement être soumise à une ou plusieurs extractions liquide/liquide avec les solvants précités sans ajout supplémentaire d'alcool (plusieurs étages d'extraction).
Afin de récupérer l'ester de l'acide fluoré formé, le procédé de l'invention peut comprendre en outre au moins une étape de récupération de l'ester de l'acide fluoré par distillation du mélange solvant organique/ester de l'acide fluoré issu de l'étape de séparation. In another embodiment, the recovered aqueous phase may optionally be subjected to one or more liquid / liquid extractions with the abovementioned solvents without additional addition of alcohol (several extraction stages). In order to recover the ester of the fluorinated acid formed, the process of the invention may further comprise at least one step of recovering the ester of the fluorinated acid by distillation of the organic solvent / acid ester mixture. fluorinated from the separation step.
Cette étape de distillation peut être mise en œuvre par toute méthode connue de l'homme du métier et notamment selon les variantes et modes de réalisation décrits plus haut. This distillation step can be implemented by any method known to those skilled in the art and in particular according to the variants and embodiments described above.
Dans le cas où l'alcool utilisé est l'éthanol, la fraction dont le point d'ébullition est compris entre 97 et 99°C est récupérée lors de cette distillation, elle correspond à la fraction de l'ester de l'acide fluoré présentant une pureté supérieure à 90%, de préférence supérieure à 95%, de manière plus préférée proche de 99%. In the case where the alcohol used is ethanol, the fraction whose boiling point is between 97 and 99 ° C. is recovered during this distillation, it corresponds to the fraction of the ester of the fluorinated acid having a purity greater than 90%, preferably greater than 95%, more preferably close to 99%.
De façon avantageuse, la fraction de solvant organique, obtenue en tête de colonne dans le cas d'un solvant organique présentant une température d'ébullition inférieure à 90°C, ou obtenue en pied de colonne dans le cas d'un solvant organique présentant une température d'ébullition supérieure à 100°C, peut être recyclée à l'étape d'estérification du procédé de l'invention. Advantageously, the organic solvent fraction, obtained at the top of the column in the case of an organic solvent having a boiling point of less than 90 ° C., or obtained at the bottom of the column in the case of an organic solvent exhibiting a boiling temperature above 100 ° C, can be recycled to the esterification step of the process of the invention.
De façon avantageuse, les fractions contenant l'ester de l'acide fluoré insuffisamment pures et l'alcool peuvent être recyclées à l'étape d'estérification du procédé de l'invention. Advantageously, the fractions containing the insufficiently pure fluorinated acid ester and the alcohol may be recycled to the esterification step of the process of the invention.
Cette étape de distillation peut être précédée d'une étape de flash distillation permettant d'obtenir un milieu organique concentré en ester de l'acide acétique fluoré. Cette étape de distillation flash est de préférence mise en œuvre à pression atmosphérique, dans une colonne de distillation comprenant moins de 10 étages théoriques, un taux de flux R inférieur à 5. This distillation step may be preceded by a flash distillation step to obtain a concentrated organic medium ester of fluorinated acetic acid. This flash distillation step is preferably carried out at atmospheric pressure, in a distillation column comprising less than 10 theoretical stages, a flow rate R less than 5.
Selon un mode de réalisation particulier, l'invention concerne un procédé de préparation d'un ester à partir d'un acide fluoré mettant en œuvre le procédé de l'invention. According to a particular embodiment, the invention relates to a process for preparing an ester from a fluorinated acid implementing the method of the invention.
La présente invention concerne par conséquent également un procédé de préparation d'un ester d'acide fluoré comprenant le traitement d'une solution aqueuse comprenant un sel d'un composé organique comprenant au moins une fonction acide et au moins un atome de fluor, dit acide fluoré, par réaction entre ledit sel, un alcool et au moins un acide de Brônsted en présence d'un solvant organique solubilisant le produit qui se forme, ledit solvant organique formant au moins un milieu réactionnel biphasique liquide/liquide avec la solution aqueuse.
Les modes de réalisation et modes préférés décrits ci-dessus s'appliquent également au procédé de préparation de l'ester d'acide fluoré. The present invention therefore also relates to a method for preparing a fluorinated acid ester comprising treating an aqueous solution comprising a salt of an organic compound comprising at least one acid function and at least one fluorine atom, said fluorinated acid, by reaction between said salt, an alcohol and at least one Brönsted acid in the presence of an organic solvent solubilizing the product that is formed, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution. The embodiments and preferred modes described above also apply to the process for preparing the fluorinated acid ester.
Le procédé de la présente invention va maintenant être décrit à l'aide d'exemples non limitatifs. La température est exprimée en degré Celsius et est celle ambiante (20- 25°C), sauf indication contraire. La pression est celle atmosphérique, sauf indication contraire. The method of the present invention will now be described by way of non-limiting examples. The temperature is expressed in degrees Celsius and is the ambient temperature (20-25 ° C) unless stated otherwise. The pressure is atmospheric unless otherwise indicated.
Exemple 1 : Example 1
Dans un réacteur en verre équipé d'une double enveloppe et d'une turbine de In a glass reactor equipped with a double jacket and a turbine of
Rushton, sont ajoutés 574,7g d'une solution aqueuse contenant 14,4% en poids de diflu oroacétate de sodium et 9% en poids de chlorure de sodium ainsi que 126g d'acide sulfurique concentré à 98% en poids. L'acide sulfurique est ajouté en 1 heure de façon à maintenir la température inférieure à 50°C. Après retour à température ambiante, 207g de xylène (mélange d'isomères o-, m-, p-) et 39,7g d'éthanol sont ajoutés. Le milieu est agité à 850rpm pendant une heure à température ambiante. L'agitation est ensuite stoppée et la phase organique supérieure est récupérée par décantation. Deux opérations d'extraction liquide liquide supplémentaires sont réalisées à partir de la solution aqueuse obtenue, avec l'ajout de deux fois 207 g de xylènes. Rushton is added 574.7 g of an aqueous solution containing 14.4% by weight of sodium difluoroacetate and 9% by weight of sodium chloride as well as 126 g of concentrated sulfuric acid at 98% by weight. Sulfuric acid is added in 1 hour so as to keep the temperature below 50 ° C. After returning to ambient temperature, 207 g of xylene (o-, m-, p- isomer mixture) and 39.7 g of ethanol are added. The medium is stirred at 850 rpm for one hour at room temperature. The stirring is then stopped and the upper organic phase is recovered by decantation. Two additional liquid liquid extraction operations are carried out from the aqueous solution obtained, with the addition of twice 207 g of xylenes.
Les phases organiques récupérées sont rassemblées (m=720,1 g) et placées dans un bouilleur de distillation équipé d'une colonne contenant 20 étages théoriques. La distillation est conduite à pression atmosphérique. La fraction ayant un point d'ébullition compris entre 98°C et 99°C est récoltée. La fraction obtenue m=70,1 g est constituée de DFAE pur à 98,7% en poids. Le rendement est de 80%. The recovered organic phases are combined (m = 720.1 g) and placed in a distillation boiler equipped with a column containing 20 theoretical stages. Distillation is conducted at atmospheric pressure. The fraction having a boiling point between 98 ° C and 99 ° C is harvested. The fraction obtained m = 70.1 g consists of pure FDFA at 98.7% by weight. The yield is 80%.
Exemple 2 : Example 2
Dans un réacteur en verre équipé d'une double enveloppe et d'une turbine de Rushton, sont ajoutés 475,3g d'une solution aqueuse contenant 13% en poids de diflu oroacétate de sodium ainsi que 165g d'acide sulfurique concentré à 98% en poids. L'acide est ajouté en 1 heure de façon à maintenir la température inférieure à 50°C. Après retour à température ambiante, 224g d'o-dichlorobenzène et 45g d'éthanol sont ajoutés. Le milieu est agité à 850rpm pendant une heure à température ambiante. L'agitation est ensuite stoppée et la phase organique inférieure est récupérée par décantation. Une seconde opération d'extraction liquide liquide est réalisée dans les mêmes conditions à partir de la solution aqueuse obtenue précédemment, avec l'ajout de 201 g de dichlorobenzène supplémentaire. Une analyse RMN 1H et 19F indique que la conversion
du difluoroacétate de sodium est de 92%. Une analyse par chromatographie en phase gazeuse montre que 89% du difluoroacétate d'éthyle théorique est présent en solution organique. Ces solutions organiques obtenues (m= 500,3g) sont réunies et distillées à pression atmosphérique sur une colonne équipée de 20 étages théoriques, avec un taux de reflux variant de 15 à 3. Une fraction de 28,3g ayant un point d'ébullition compris entre 97,5 et 99°C est recueillie. La concentration en difluoroacétate d'éthyle est supérieure à 97% en poids. Le rendement de la réaction est de 51 %. Une seconde distillation de cette fraction permet d'obtenir le difluoroacétate d'éthyle avec une pureté supérieure à 99,5% en poids. Ce rendement de 51 % peut être amélioré à plus de 80% en recyclant les fractions impures d'ester de DFA contenant de l'alcool comme précisé plus haut. In a glass reactor equipped with a jacket and a Rushton turbine, are added 475.3 g of an aqueous solution containing 13% by weight of sodium difluoacetate and 165 g of 98% concentrated sulfuric acid. in weight. The acid is added in 1 hour to maintain the temperature below 50 ° C. After returning to ambient temperature, 224 g of o-dichlorobenzene and 45 g of ethanol are added. The medium is stirred at 850 rpm for one hour at room temperature. The stirring is then stopped and the lower organic phase is recovered by decantation. A second liquid liquid extraction operation is carried out under the same conditions from the aqueous solution obtained above, with the addition of 201 g of additional dichlorobenzene. 1 H NMR and 19 F analysis indicate that the conversion sodium difluoroacetate is 92%. Gas chromatographic analysis shows that 89% of the theoretical ethyl difluoroacetate is present in organic solution. These organic solutions obtained (m = 500.3 g) are combined and distilled at atmospheric pressure on a column equipped with 20 theoretical stages, with a reflux ratio ranging from 15 to 3. A fraction of 28.3 g having a boiling point between 97.5 and 99 ° C is collected. The concentration of ethyl difluoroacetate is greater than 97% by weight. The yield of the reaction is 51%. A second distillation of this fraction makes it possible to obtain ethyl difluoroacetate with a purity greater than 99.5% by weight. This yield of 51% can be improved to more than 80% by recycling the impure fractions of DFA ester containing alcohol as specified above.
Exemple 3 : Example 3
Dans un réacteur en PTFE équipé d'une turbine de Rushton, est ajouté 8,7g de difluoroacétate de potassium, 43,8g de fluorure de potassium, 6,3g de chlorure de potassium et 1 15g d'acide chlorhydrique concentré à 37%. Après retour à température ambiante, 9g d'éthanol et 190g d'o-xylène sont ajoutés et l'agitation est maintenue 1 heure à 850 rpm. La phase supérieure est ensuite récupérée par décantation. Deux extractions liquide/liquide supplémentaires de la phase aqueuse sont réalisées en ajoutant deux fois 190g d'o-xylène. Une mesure par RMN 1H et 19F indique que le taux de conversion du difluoroacétate de potassium présent en phase aqueuse est de 93%. L'analyse des phases organiques par chromatographie en phase gazeuse indique que le rendement en difluoroacétate d'éthyle extrait est de 88%. Les phases organiques sont rassemblées et distillées à pression atmosphérique à l'aide d'une colonne comportant 20 étages théoriques. La fraction ayant un point d'ébullition compris entre 98 et 98,5°C est récupérée. Elle correspond au difluoroacétate d'éthyle ayant une pureté de 99% en poids. In a PTFE reactor equipped with a Rushton turbine is added 8.7 g of potassium difluoroacetate, 43.8 g of potassium fluoride, 6.3 g of potassium chloride and 1 g of 37% concentrated hydrochloric acid. After returning to ambient temperature, 9 g of ethanol and 190 g of o-xylene are added and stirring is maintained for 1 hour at 850 rpm. The upper phase is then recovered by decantation. Two additional liquid / liquid extractions from the aqueous phase are carried out by adding 190 g of o-xylene twice. Measurement by 1 H NMR and 19 F indicates that the conversion rate of potassium difluoroacetate present in the aqueous phase is 93%. Analysis of the organic phases by gas chromatography indicates that the yield of ethyl difluoroacetate extracted is 88%. The organic phases are combined and distilled at atmospheric pressure using a column comprising 20 theoretical stages. The fraction having a boiling point between 98 and 98.5 ° C is recovered. It corresponds to ethyl difluoroacetate having a purity of 99% by weight.
Exemple 4 : Example 4
Dans un réacteur en verre équipé d'une turbine de Rushton, sont ajoutés 483g d'une solution aqueuse contenant 15% en poids de trifluoroacétate de sodium et 165g d'acide sulfurique concentré. L'acide est ajouté en 1 heure de façon à maintenir la température inférieure à T=50°C. Après retour à une température de 20°C, 190g d'o- xylène et 33g d'éthanol sont ajoutés et le milieu est maintenu sous agitation pendant 1 heure. Après décantation, la phase organique (supérieure) est récupérée et la phase aqueuse est extraite une seconde fois avec 200g d'o-xylène. Les deux phases organiques sont rassemblées. Une analyse par chromatographie en phase gazeuse montre que 83% du trifluoroacétate d'éthyle attendu est présent en solution organique. Cette solution est
distillée à pression atmosphérique sur une colonne équipée de 20 étages théoriques. La fraction ayant un point d'ébullition compris entre 60°C et 62°C est recueillie. La pureté du trifluoroacétate d'éthyle est de 91 % en poids. Exemple 5 : In a glass reactor equipped with a Rushton turbine, are added 483 g of an aqueous solution containing 15% by weight of sodium trifluoroacetate and 165 g of concentrated sulfuric acid. The acid is added in 1 hour to maintain the temperature below T = 50 ° C. After returning to a temperature of 20 ° C., 190 g of o-xylene and 33 g of ethanol are added and the medium is stirred for 1 hour. After decantation, the organic phase (upper) is recovered and the aqueous phase is extracted a second time with 200 g of o-xylene. The two organic phases are combined. Analysis by gas chromatography shows that 83% of the expected ethyl trifluoroacetate is present in organic solution. This solution is distilled at atmospheric pressure on a column equipped with 20 theoretical stages. The fraction having a boiling point between 60 ° C and 62 ° C is collected. The purity of ethyl trifluoroacetate is 91% by weight. Example 5
Dans un réacteur contenant 24,5g de 3,3,3-trifluoropropanoate de potassium et 38,7g de chlorure de potassium en solution dans 217 mL d'eau sont ajoutés 30g d'une solution d'acide chlorhydrique concentré (37%) , 13,6g d'éthanol et 70g de p-xylène. L'agitation est maintenue pendant 30 minutes à température ambiante. Les deux phases sont ensuite séparées et la phase aqueuse est extraite deux fois supplémentaires avec 70g de p-xylène. Les couches organiques sont ensuite rassemblées. On obtient 347g d'une solution organique contenant 6,1 % en poids de 3,3,3-trifluoropropanoate d'éthyle. In a reactor containing 24.5 g of potassium 3,3,3-trifluoropropanoate and 38.7 g of potassium chloride in solution in 217 ml of water are added 30 g of a concentrated hydrochloric acid solution (37%), 13.6g of ethanol and 70g of p-xylene. Stirring is maintained for 30 minutes at room temperature. The two phases are then separated and the aqueous phase is extracted twice more with 70 g of p-xylene. The organic layers are then collected. 347 g of an organic solution containing 6.1% by weight of 3,3,3-trifluoropropanoate of ethyl are obtained.
Exemple 6 : Example 6
A une solution de 81 ,4g d'acide 2-fluoropropanoïque, 162g de fluorure de potassium, 65,9g de chlorure de potassium dans 249g d'eau est ajoutée une solution d'acide chlorhydrique concentré (363g en maintenant la température inférieure à T=35°C. Du méthanol (59g) et du mésitylène (492g) sont ensuite ajoutés et l'ensemble est laissé sous agitation pendant 30 minutes. Les phases sont séparées et la solution aqueuse est extraite deux fois supplémentaires avec 492g de mésitylène. L'ensemble des solutions organiques obtenues sont rassemblées et l'on obtient ainsi 1515g d'une solution organique contenant 81 ,6g de 2-fluoropropanoate de méthyle. Le rendement en 2- fluoropropanoate de méthyle est de 84%. Cet ester est obtenu pur après distillation sous pression réduite.
To a solution of 81.4 g of 2-fluoropropanoic acid, 162 g of potassium fluoride, 65.9 g of potassium chloride in 249 g of water is added a solution of concentrated hydrochloric acid (363 g keeping the temperature below T = 35 ° C. Methanol (59 g) and mesitylene (492 g) are then added and the mixture is left stirring for 30 minutes The phases are separated and the aqueous solution is extracted twice more with 492 g of mesitylene. The organic solutions obtained are combined to give 1515 g of an organic solution containing 81.6 g of methyl 2-fluoropropanoate.The yield of methyl 2-fluoropropanoate is 84%. distillation under reduced pressure.
Claims
Revendications claims
'\ - Procédé de traitement d'une solution aqueuse comprenant un sel d'un composé organique comprenant au moins une fonction acide et au moins un atome de fluor, dit acide fluoré, par réaction entre ledit sel, au moins un acide de Brônsted et un alcool en présence d'un solvant organique solubilisant le produit qui se forme, ledit solvant organique formant au moins un milieu réactionnel biphasique liquide/liquide avec la solution aqueuse. A process for treating an aqueous solution comprising a salt of an organic compound comprising at least one acidic function and at least one fluorine atom, said fluoro acid, by reaction between said salt, at least one Brönsted acid and an alcohol in the presence of an organic solvent solubilizing the product that is formed, said organic solvent forming at least one biphasic liquid / liquid reaction medium with the aqueous solution.
2. - Procédé selon la revendication 1 , dans lequel l'acide fluoré est choisi parmi les acides carboxyliques fluorés solubles dans l'eau. 2. - Process according to claim 1, wherein the fluorinated acid is selected from fluorinated carboxylic acids soluble in water.
3. - Procédé selon la revendication 1 ou 2, dans lequel l'acide fluoré est choisi parmi les acides carboxyliques aliphatiques comprenant au moins un atome de fluor et comprenant de 2 à 15 atomes de carbone. 3. - Process according to claim 1 or 2, wherein the fluorinated acid is selected from aliphatic carboxylic acids comprising at least one fluorine atom and comprising from 2 to 15 carbon atoms.
4. - Procédé selon la revendication 1 ou 2, dans lequel l'acide fluoré est un acide acétique fluoré. 4. - Process according to claim 1 or 2, wherein the fluorinated acid is a fluorinated acetic acid.
5. - Procédé selon l'une des revendications 1 à 4, dans lequel la solution aqueuse comprend en outre un ou plusieurs sels inorganiques de formule MX, dans laquelle X est un atome d'halogène, notamment fluor ou chlore ; et M est un élément choisi parmi les éléments des colonnes 1 à 12 du tableau périodique des éléments. 5. - Method according to one of claims 1 to 4, wherein the aqueous solution further comprises one or more inorganic salts of formula MX, wherein X is a halogen atom, especially fluorine or chlorine; and M is an element chosen from the elements of columns 1 to 12 of the periodic table of the elements.
6. - Procédé selon l'une des revendications 1 à 5, dans lequel l'alcool est de formule R1OH où R1 représente un groupe alkyle, linéaire ou ramifié, comprenant de 1 à 10 atomes de carbone, de préférence de 1 à 5 atomes de carbone, par exemple méthyle, éthyle, propyle, isopropyle, butyle, pentyle et isopentyle. 6. - Method according to one of claims 1 to 5, wherein the alcohol is of formula R 1 OH wherein R 1 represents a linear or branched alkyl group comprising 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, pentyl and isopentyl.
7. - Procédé selon l'une quelconque des revendications 1 ou 6, dans lequel l'alcool est l'éthanol. 7. - Process according to any one of claims 1 or 6, wherein the alcohol is ethanol.
8. - Procédé selon l'une quelconque des revendications 1 à 7, dans lequel l'acide de Brônsted est choisi parmi HCI gazeux ou en solution, H2S04, H3P04, HN03 ou HBr, pur ou dilué ou l'un quelconque de leurs mélanges.
8. - Process according to any one of claims 1 to 7, wherein the Brönsted acid is selected from HCl gas or in solution, H 2 S0 4 , H 3 P0 4 , HN0 3 or HBr, pure or diluted or any of their mixtures.
9.- Procédé selon l'une quelconque des revendications 1 à 8, dans lequel le solvant est choisi parmi les solvants apolaires et l'un quelconque de leurs mélanges. 9. A process according to any one of claims 1 to 8, wherein the solvent is selected from apolar solvents and any of their mixtures.
10.- Procédé selon la revendication 9, dans lequel le solvant est choisi parmi les solvants aromatiques, les solvants aliphatiques chlorés, les éthers d'alkyle ou l'un quelconque de leurs mélanges. 10. The process according to claim 9, wherein the solvent is selected from aromatic solvents, chlorinated aliphatic solvents, alkyl ethers or any of their mixtures.
1 1.- Procédé selon la revendication 10, dans lequel le solvant aromatique est choisi parmi est choisi parmi le xylène (ortho, meta ou para), le toluène, le chlorobenzène, le dichlorobenzène, le mésithylène, le méthoxybenzène (anisole), le 1 ,2-diméthoxybenzène (vératrole), l'éthylbenzène, le trifluorométhylbenzène, ou l'un quelconque de leurs mélanges. The process according to claim 10, wherein the aromatic solvent is selected from among xylene (ortho, meta or para), toluene, chlorobenzene, dichlorobenzene, mesithylene, methoxybenzene (anisole), 1,2-dimethoxybenzene (veratrole), ethylbenzene, trifluoromethylbenzene, or any of their mixtures.
12.- Procédé selon la revendication 10, dans lequel le solvant aliphatique chloré est choisi parmi le dichlorométhane, le dichloroéthane, le chloroforme, ou l'un quelconque de leurs mélanges. 12. The process of claim 10, wherein the chlorinated aliphatic solvent is selected from dichloromethane, dichloroethane, chloroform, or any of their mixtures.
13. - Procédé selon la revendication 10, pour lequel le solvant éther d'alkyle est choisi parmi le méthyltertiobutyl éther (MTBE) ou le diisobutyléther, ou leur mélange. 13. - The method of claim 10, wherein the alkyl ether solvent is selected from methyltertiobutyl ether (MTBE) or diisobutylether, or their mixture.
14. - Procédé selon l'une quelconque des revendications 1 à 13, dans lequel l'alcool est utilisé dans une proportion de 1 à 5 équivalents molaires par rapport au sel d'acide fluoré. 14. - Process according to any one of claims 1 to 13, wherein the alcohol is used in a proportion of 1 to 5 molar equivalents relative to the fluorinated acid salt.
15.- Procédé selon l'une quelconque des revendications 1 à 14, dans lequel le solvant est utilisé dans une proportion de 50 à 200% en volume par rapport au volume de la solution aqueuse. 15. A process according to any one of claims 1 to 14, wherein the solvent is used in a proportion of 50 to 200% by volume relative to the volume of the aqueous solution.
16. - Procédé selon l'une quelconque des revendications 1 à 15, comprenant en outre au moins une étape de séparation du mélange solvant/produit formé de la solution aqueuse. 16. - Process according to any one of claims 1 to 15, further comprising at least one step of separating the solvent / product mixture formed from the aqueous solution.
17. - Procédé selon la revendication 13, comprenant en outre au moins une étape de récupération du produit formé par distillation du mélange solvant/produit formé. 17. - The method of claim 13, further comprising at least one step of recovering the product formed by distillation of the solvent / product mixture formed.
18.- Procédé selon la revendication 17 comprenant en outre une étape de distillation flash suivie d'une étape de distillation.
18. The method of claim 17 further comprising a flash distillation step followed by a distillation step.
19.- Procédé selon l'une quelconque des revendications 1 à 13, dans lequel l'acide fluoré est l'acide difluoroacétique est le produit formé est un ester de l'acide difluoroacétique.19. A process according to any one of claims 1 to 13, wherein the fluorinated acid is difluoroacetic acid is the product formed is an ester of difluoroacetic acid.
5
5
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1259372A FR2996147B1 (en) | 2012-10-03 | 2012-10-03 | PROCESS FOR TREATING FLUID ACID |
| PCT/EP2013/069267 WO2014053312A1 (en) | 2012-10-03 | 2013-09-17 | Method for processing fluoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2903960A1 true EP2903960A1 (en) | 2015-08-12 |
Family
ID=47624247
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP13762846.7A Withdrawn EP2903960A1 (en) | 2012-10-03 | 2013-09-17 | Method for processing fluoric acid |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9394225B2 (en) |
| EP (1) | EP2903960A1 (en) |
| JP (1) | JP2015533823A (en) |
| CN (1) | CN104684884B (en) |
| CA (1) | CA2886790A1 (en) |
| FR (1) | FR2996147B1 (en) |
| IN (1) | IN2015DN02362A (en) |
| WO (1) | WO2014053312A1 (en) |
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| CN110343043A (en) * | 2018-04-04 | 2019-10-18 | 浙江蓝天环保高科技股份有限公司 | A kind of purification process of Trifluoroacetic Acid Ethyl Ester |
| CN110872226A (en) * | 2019-12-05 | 2020-03-10 | 常熟三爱富中昊化工新材料有限公司 | Preparation process of trifluoroacetic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5826843A (en) * | 1981-08-11 | 1983-02-17 | Sumitomo Chem Co Ltd | Preparation of acrylic or methacrylic ester |
| US6720447B1 (en) * | 1999-02-03 | 2004-04-13 | Basf Aktiengesellschaft | Method for the production of esters |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS563338A (en) * | 1979-06-20 | 1981-01-14 | Toshiba Corp | Energy accumulator having fly-wheel |
| FR2605315B1 (en) * | 1986-10-16 | 1988-12-02 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF ETHYL TRIFLUOROACETATE. |
| JPH07100676B2 (en) * | 1987-08-31 | 1995-11-01 | セントラル硝子株式会社 | Method for producing fluorcarbone carboxylic acid |
| DE4402694A1 (en) * | 1993-06-02 | 1995-08-03 | Hoechst Ag | Process for the recovery of fluorinated carboxylic acids |
| US6248923B1 (en) * | 1999-09-03 | 2001-06-19 | Eastman Chemical Company | Process for the production of fluorocarboxylic acid anhydrides |
| CN100381366C (en) * | 2002-06-19 | 2008-04-16 | 笹仓机械工程有限公司 | Method for recovering fluorine-containing emulsifier |
| JP2008162902A (en) * | 2006-12-27 | 2008-07-17 | Central Glass Co Ltd | Method for producing difluoroacetic acid ester |
| WO2009157416A1 (en) * | 2008-06-24 | 2009-12-30 | 旭硝子株式会社 | Fluorine-containing compound purification method |
| FR2933693B1 (en) | 2008-07-10 | 2010-09-03 | Rhodia Operations | PROCESS FOR SEPARATING CARBOXYLIC ACID IN SALIENT FORM CARRIER OF AT LEAST ONE HALOGEN ATOM |
| FR2947264B1 (en) * | 2009-06-30 | 2012-08-10 | Rhodia Operations | PROCEDURE FOR THE PREPARATION OF DIFLUOROACETIC ACID |
| CN103201245B (en) * | 2010-11-08 | 2015-09-16 | 索尔维特殊聚合物意大利有限公司 | Prepare the method for difluoroacetic acid |
-
2012
- 2012-10-03 FR FR1259372A patent/FR2996147B1/en not_active Expired - Fee Related
-
2013
- 2013-09-17 JP JP2015534950A patent/JP2015533823A/en active Pending
- 2013-09-17 CN CN201380052066.9A patent/CN104684884B/en not_active Expired - Fee Related
- 2013-09-17 EP EP13762846.7A patent/EP2903960A1/en not_active Withdrawn
- 2013-09-17 CA CA2886790A patent/CA2886790A1/en not_active Abandoned
- 2013-09-17 US US14/429,442 patent/US9394225B2/en not_active Expired - Fee Related
- 2013-09-17 WO PCT/EP2013/069267 patent/WO2014053312A1/en active Application Filing
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- 2015-03-23 IN IN2362DEN2015 patent/IN2015DN02362A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5826843A (en) * | 1981-08-11 | 1983-02-17 | Sumitomo Chem Co Ltd | Preparation of acrylic or methacrylic ester |
| US6720447B1 (en) * | 1999-02-03 | 2004-04-13 | Basf Aktiengesellschaft | Method for the production of esters |
Non-Patent Citations (1)
| Title |
|---|
| See also references of WO2014053312A1 * |
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| CA2886790A1 (en) | 2014-04-10 |
| US9394225B2 (en) | 2016-07-19 |
| WO2014053312A1 (en) | 2014-04-10 |
| FR2996147A1 (en) | 2014-04-04 |
| JP2015533823A (en) | 2015-11-26 |
| CN104684884A (en) | 2015-06-03 |
| FR2996147B1 (en) | 2015-05-29 |
| CN104684884B (en) | 2018-02-06 |
| US20150232408A1 (en) | 2015-08-20 |
| IN2015DN02362A (en) | 2015-09-04 |
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