EP3807240A1 - Method for producing 2-chloro-3,3,3-trifluoropropene and facility for implementing same - Google Patents
Method for producing 2-chloro-3,3,3-trifluoropropene and facility for implementing sameInfo
- Publication number
- EP3807240A1 EP3807240A1 EP19745192.5A EP19745192A EP3807240A1 EP 3807240 A1 EP3807240 A1 EP 3807240A1 EP 19745192 A EP19745192 A EP 19745192A EP 3807240 A1 EP3807240 A1 EP 3807240A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- fixed bed
- weight
- less
- stream
- 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.)
- Pending
Links
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- PQUUGVDRLWLNGR-UHFFFAOYSA-N 2,3,3,3-tetrachloroprop-1-ene Chemical compound ClC(=C)C(Cl)(Cl)Cl PQUUGVDRLWLNGR-UHFFFAOYSA-N 0.000 claims abstract description 6
- QJMGASHUZRHZBT-UHFFFAOYSA-N 2,3-dichloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)C(Cl)CCl QJMGASHUZRHZBT-UHFFFAOYSA-N 0.000 claims abstract description 6
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical compound ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000009434 installation Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000011810 insulating material Substances 0.000 claims description 10
- ZXPCCXXSNUIVNK-UHFFFAOYSA-N 1,1,1,2,3-pentachloropropane Chemical compound ClCC(Cl)C(Cl)(Cl)Cl ZXPCCXXSNUIVNK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 5
- 235000012241 calcium silicate Nutrition 0.000 claims description 5
- 230000001413 cellular effect Effects 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000011491 glass wool Substances 0.000 claims description 5
- 239000012212 insulator Substances 0.000 claims description 5
- 239000000391 magnesium silicate Substances 0.000 claims description 5
- 239000011490 mineral wool Substances 0.000 claims description 5
- 239000010451 perlite Substances 0.000 claims description 5
- 235000019362 perlite Nutrition 0.000 claims description 5
- 239000010455 vermiculite Substances 0.000 claims description 5
- 229910052902 vermiculite Inorganic materials 0.000 claims description 5
- 235000019354 vermiculite Nutrition 0.000 claims description 5
- 238000005304 joining Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 19
- IAOGXBHBKZGVGJ-UHFFFAOYSA-N 2,3,3-trichloro-3-fluoroprop-1-ene Chemical compound FC(Cl)(Cl)C(Cl)=C IAOGXBHBKZGVGJ-UHFFFAOYSA-N 0.000 description 12
- IAPGBTZUBKUKOR-UHFFFAOYSA-N 2,3-dichloro-3,3-difluoroprop-1-ene Chemical compound FC(F)(Cl)C(Cl)=C IAPGBTZUBKUKOR-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- FDOPVENYMZRARC-UHFFFAOYSA-N 1,1,1,2,2-pentafluoropropane Chemical compound CC(F)(F)C(F)(F)F FDOPVENYMZRARC-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- QCMJBECJXQJLIL-UHFFFAOYSA-L chromium(6+);oxygen(2-);difluoride Chemical compound [O-2].[O-2].[F-].[F-].[Cr+6] QCMJBECJXQJLIL-UHFFFAOYSA-L 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- -1 hydrofluoroolefins Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IYFMQUDCYNWFTL-UHFFFAOYSA-N 1,1,2,2,3-pentachloropropane Chemical compound ClCC(Cl)(Cl)C(Cl)Cl IYFMQUDCYNWFTL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- GVVUPGXFVJLPDE-OWOJBTEDSA-N (e)-1,3,3,3-tetrachloroprop-1-ene Chemical compound Cl\C=C\C(Cl)(Cl)Cl GVVUPGXFVJLPDE-OWOJBTEDSA-N 0.000 description 1
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 101100004392 Arabidopsis thaliana BHLH147 gene Proteins 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical class CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 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
- 239000008204 material by function Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
- B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00026—Controlling or regulating the heat exchange system
- B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
- B01J2208/00044—Temperature measurement
- B01J2208/00061—Temperature measurement of the reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00477—Controlling the temperature by thermal insulation means
- B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00522—Controlling the temperature using inert heat absorbing solids outside the bed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
- B01J2219/00063—Temperature measurement of the reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/0015—Controlling the temperature by thermal insulation means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
- B01J2219/0236—Metal based
Definitions
- the present invention relates to the production of hydrofluoroolefins, in particular the present invention relates to the production of 2-chloro-3,3,3-trifluoropropene.
- Halogenated hydrocarbons in particular fluorinated hydrocarbons such as hydrofluoroolefins, are compounds which have a useful structure as functional materials, solvents, refrigerants, blowing agents and monomers for functional polymers or starting materials for such monomers.
- Hydrofluorolefins like 2,3,3,3-tetrafluoropropene (HFO-1234yf) attract attention because they offer promising behavior as refrigerants with low global warming potential.
- the processes for producing fluoroolefins are usually carried out in the presence of a starting material such as an alkane containing chlorine or an alkene containing chlorine, and in the presence of a fluorinating agent such as hydrogen fluoride. These processes can be carried out in the gas phase or in the liquid phase, without or without the catalyst.
- a starting material such as an alkane containing chlorine or an alkene containing chlorine
- a fluorinating agent such as hydrogen fluoride.
- HCFO-1233xf 2-chloro-3,3,3-trifluoropropene
- HCC- 240db 1,1,1,2,3- pentachloropropane
- a process for the preparation of 2,3,3,3-tetrafluoropropene from 1,1,1,2,3-pentachloropropane and / or 1, 1,2, 2,3- pentachloropropane comprising the stages: (a) catalytic reaction of 1,1,1,2,3-pentachloropropane and / or 1,1,2,2,3-pentachloropropane with HF to a reaction mixture comprising HCl, 2-chloro- 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, unreacted HF and optionally 1,1,1,2,2-pentafluoropropane; (b) separation of the reaction mixture into a first stream comprising HCl and 2,3,3,3-tetrafluoropropene and a second stream comprising HF, 2-chloro-3,3,3-trifluoropropene and optionally 1,1,1,2 , 2- pentafluoro
- control and control of the reaction temperature is an important parameter which makes it possible to achieve the reaction kinetics, the conversions and the selectivities. This is also particularly recommended in order to avoid thermal decompositions of thermally sensitive compounds which may impact the activity of the catalyst by the formation of coke and thus considerably reduce the lifetime of the catalyst.
- a multitubular reactor is by definition the ideal insulated reactor to be able to control the reaction temperature and obtain the most homogeneous reaction temperature possible since the catalyst is distributed in tubes and a fluid can circulate in the shell around the tubes to either remove reaction heat in the event of an exothermic reaction, or provide heat in the event of an endothermic reaction.
- the production of a multitubular reactor may prove to be impossible since it would require too many tubes and a homogeneous distribution of the gases in each of the tubes is therefore very difficult. to achieve.
- adiabatic fixed bed reactor does not exhibit heat exchange with an external medium by definition.
- the adiabatic reactor is characterized by an inhomogeneous temperature at any point of the fixed bed and thus, by a temperature gradient both radial and longitudinal, due to the reaction heats and heat losses at the external walls of the reactor.
- Document US 2016/0347692 describes the implementation of a radical production process in homogeneous gas phase of chlorinated or fluorinated propene in an adiabatic flow reactor controlling the turbulence of the flows entering the reactor.
- the present invention relates to a process for the production of 2-chloro-3,3,3-trifluoropropene comprising the steps:
- a stream A comprising at least one chlorinated compound selected from the group consisting of 2,3-dichloro-1,1,1-trifluoropropane, 1,1,1,2,3-pentachloropropane,
- an adiabatic reactor comprising a fixed bed composed of an inlet and an outlet, bringing said stream A into contact with HF in the presence or not of a catalyst to produce a stream B comprising 2-chloro-3,3 , 3-trifluoropropene,
- the temperature at the inlet of the fixed bed of said adiabatic reactor is between 300 ° C and 400 ° C and the longitudinal temperature difference between the inlet of the fixed bed and the outlet of the fixed bed of said reactor is less than 20 ° C.
- the value of the longitudinal temperature difference is considered in absolute value.
- the temperature at the inlet of the fixed bed of said reactor is between 340 ° C and 380 ° C and the longitudinal temperature difference between the inlet of the fixed bed of said reactor and the outlet of the fixed bed of said reactor is below 20 ° C.
- the HF / chlorinated compounds molar ratio is adjusted so as to keep the longitudinal temperature difference between the inlet of the fixed bed and the outlet of the fixed bed of the reactor less than 20 ° C.
- the HF / chlorinated compounds molar ratio is greater than or equal to 5, advantageously greater than or equal to 10, preferably greater than or equal to 12.
- said reactor comprises side walls comprising an interior layer, an intermediate layer disposed on said interior layer and an insulating layer disposed on said intermediate layer; and the difference in radial temperature between a point located in the center of the fixed bed of said reactor and a point located in the radial plane at the level of the inner layer of the side wall of said reactor is less than 10 ° C.
- Said inner layer is that in contact with the reagents.
- the value of the radial temperature difference is considered as an absolute value.
- said reactor comprises side walls comprising an interior layer, an intermediate layer disposed on said interior layer and an insulating layer disposed on said intermediate layer; said insulating layer being made of an M2 heat-insulating material whose thickness varies between 1 mm and 500 mm.
- the M2 heat-insulating material is selected from the group consisting of rock wool, glass wool, silicate fibers, calcium-magnesium silicates, calcium silicates, microporous insulators, cellular glass , expanded perlite, exfoliated vermiculite.
- the pressure at the inlet of said reactor is between 3 and 15 bara.
- At least part of said stream B is recycled in step i) and said at least part of said stream B recycled has an electrical conductivity of less than 15 mS / cm.
- the present invention relates to an installation for manufacturing 2-chloro-3,3,3-trifluoropropene, comprising:
- an adiabatic reactor comprising a bottom, a cover and side walls joining between the bottom and the cover, at least one fixed bed and at least one rod supporting one or more temperature sensor (s); said bottom, said cover and said side walls each comprise at least one inner layer, an intermediate layer disposed on said inner layer and an insulating layer disposed around said intermediate layer; said inner layer being made of an Ml material comprising a mass content of nickel of at least 30%; said intermediate layer being made of a material Ml 'comprising at least 70% by weight of iron; said insulating layer being made of an M2 heat-insulating material selected from the group consisting of rock wool, glass wool, silicate fibers, calcium-magnesium silicates, calcium silicates, microporous insulators, cellular glass, expanded perlite, exfoliated vermiculite; the length of said at least one rod supporting one or more temperature sensor (s) being at least equal to the height of said fixed bed; and said at least one rod comprising at least one temperature sensor disposed in said fixed bed.
- a reaction flow supply system for said reactor comprising a supply line for hydrofluoric acid and at least one supply line for a stream A comprising at least one of the chlorinated compounds selected from the group consisting of 2, 3-dichloro-1,1,1-trifluoropropane, 1,1,1,2,3-pentachloropropane, 1, 1,2,3-tetrachloropropene and 2,3,3,3-tetrachloropropene;
- At least one conductivity meter capable of measuring the electrical conductivity of the reaction flow entering said reactor.
- FIG. 1 schematically represents a reactor according to a particular embodiment of the present invention.
- FIG. 2 schematically represents a view in longitudinal section of a reactor according to a particular embodiment of the present invention.
- FIG. 3 schematically represents a cross-sectional view of a reactor according to a particular embodiment of the present invention.
- Figure 4 schematically shows a sectional view of the side walls of a reactor according to a particular embodiment of the present invention.
- FIG. 5 schematically represents a plant for manufacturing 2,3,3,3-tetrafluoropropene according to a particular embodiment of the present invention.
- the present invention relates to a process for the production of 2-chloro-3,3,3-trifluoropropene.
- said process for producing 2-chloro-3,3,3-trifluoropropene comprises the steps:
- a stream A comprising at least one of the chlorinated compounds selected from the group consisting of 2,3-dichloro-1,1,1-trifluoropropane, 1,1,1,2,3- pentachloropropane, 1,1 , 2,3-tetrachloropropene and 2,3,3,3-tetrachloropropene; and
- an adiabatic reactor comprising a fixed bed composed of an inlet and an outlet, bringing said stream A into contact with HF in the presence or not of a catalyst to produce a stream B comprising 2-chloro-3,3 , 3-trifluoropropene.
- the temperature at the inlet of the fixed bed of said reactor is between 300 ° C and 400 ° C and the longitudinal temperature difference between the inlet of the fixed bed and the outlet of the fixed bed of the reactor is less than 20 ° vs.
- the temperature at the inlet of the fixed bed of said reactor is between 330 ° C and 400 ° C, preferably between 330 ° C and 390 ° C, in particular between 340 ° C and 380 ° C.
- a temperature above 400 ° C can make the catalyst irreversibly inactive while a temperature below 300 ° C prevents the fluorination reaction from being carried out.
- FIG. 2 represents a schematic view in longitudinal section of a reactor 1 according to a particular embodiment of the present invention and comprising a fixed bed 5.
- the longitudinal temperature difference ATa is defined by the temperature difference between the inlet of the fixed bed 9 and the exit from the fixed bed 10.
- the longitudinal temperature difference between the inlet of the fixed bed of said reactor and the outlet of the fixed bed of said reactor is less than 20 ° C, advantageously less than 19 ° C, preferably less than 18 ° C, more preferably less at 17 ° C, in particular less than 16 ° C, more particularly less than 15 ° C, preferably less than 14 ° C, advantageously less than 13 ° C, preferably less than 12 ° C, more preferably less than 11 ° C, more preferably less than 10 ° C.
- step ii) is carried out in the presence of a catalyst, preferably a chromium-based catalyst.
- a catalyst preferably a chromium-based catalyst.
- the chromium-based catalyst can be a chromium oxide (e.g. CrÜ2, CrC> 3 or Cr2C> 3), chromium oxyfluoride or chromium fluoride (e.g. CrFs) or a mixture thereof .
- the chromium oxyfluoride may contain a fluorine content of between 1 and 60% by weight based on the total weight of the chromium oxyfluoride, advantageously between 5 and 55% by weight, preferably between 10 and 52% by weight, more preferably between 15 and 52% by weight, in particular between 20 and 50% by weight, more particularly between 25 and 45% by weight, preferably between 30 and 45% by weight, more preferably between 35 and 45% by weight of fluorine based on the total weight of chromium oxyfluoride.
- the catalyst can also comprise a co-catalyst chosen from the group consisting of Ni, Co, Zn, Mg, Mn, Fe, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb, Sb; of preferably Ni, Co, Zn, Mg, Mn; in particular Ni, Co, Zn.
- the content by weight of the cocatalyst is between 1 and 10% by weight based on the total weight of the catalyst.
- the catalyst can be supported or not.
- a support such as alumina, for example in its alpha form, activated alumina, aluminum halides (AIF3 for example), aluminum oxyhalides, activated carbon, magnesium fluoride or graphite can be used.
- the catalyst can have a specific surface area between 1 and 100 m 2 / g, preferably between 5 and 80 m 2 / g, more preferably between 5 and 70 m 2 / g, ideally between 5 and 50 m 2 / g, in particular between 10 and 50 m 2 / g, more particularly between 15 and 45 m 2 / g.
- step ii) is carried out in the absence of catalyst.
- said fixed bed contains an inert solid.
- the inert solid can be corundum, silicon carbide, quartz balls or rings, a metal lining with a metal M1 as defined in the present application or nickel balls.
- step ii) is carried out at atmospheric pressure or at a pressure greater than this, advantageously at a pressure greater than 1.5 bara, preferably at a pressure greater than 2, 0 bara, in particular at a pressure greater than 2.5 bara, more particularly at a pressure greater than 3.0 bara.
- step ii) is carried out at a pressure between atmospheric pressure and 20 bara, preferably between 2 and 18 bara, more preferably between 3 and 15 bara.
- step ii) of the present process is carried out with a contact time between 1 and 100 s, preferably between 2 and 75 s, in particular between 3 and 50 s.
- An oxidant such as oxygen or chlorine, can be added during step ii).
- the molar ratio of the oxidant to the hydrocarbon compound can be between 0.005 and 2, preferably between 0.01 and 1.5.
- the oxidant can be pure oxygen, air or a mixture of oxygen and nitrogen.
- the HF / said molar ratio of said at least one chlorinated compound is greater than or equal to 5, advantageously greater than or equal to 10, preferably greater than or equal to 12.
- the HF / molar ratio said at least one chlorinated compound is between 12: 1 and 150: 1, preferably between 12: 1 and 125: 1, more preferably between 12: 1 and 100: 1.
- the temperature within the reactor, and in particular within the fixed bed varies radially, i.e. the temperature varies between the center of the reactor and the side walls of the reactor located in the same plane, in particular between the center of the fixed bed and the side wall of the reactor located in the same plane.
- the control of the radial temperature in the fixed bed can be carried out by insulating the side walls of said reactor with an insulating material of a defined thickness.
- said side walls each comprise at least one inner layer and an insulating layer disposed around said inner layer.
- an intermediate layer is disposed between said inner layer and said insulating layer.
- FIG. 3 represents a transverse view along the section plane (a, a ') of a reactor 1 according to an embodiment of the present invention and comprising a fixed bed 5.
- the side walls 3 of said reactor comprise an inner layer 21 , an intermediate layer 22 disposed on said inner layer 21 and an insulating layer 23 disposed on said intermediate layer 22 ( Figure 4).
- the difference in radial temperature ATb is defined by the difference between a point located in the center of the fixed bed 5 of the reactor and a point 12 located in the radial plane at the level of the inner layer 21 of the side wall 3 of said reactor ( Figure 3) .
- the difference in radial temperature between a point located in the center of the fixed bed of the reactor and a point located in the radial plane at the level of the inner layer of the side wall of said reactor is less than 10 ° C, advantageously less than 9 ° C, preferably less than 8 ° C, more preferably less than 7 ° C, in particular less than 6 ° C, more particularly less than 5 ° C.
- said inner layer has a thickness of between 0.01 and 20 mm.
- said inner layer can have a thickness of between 0.05 and 15 mm, preferably between 0.1 and 10 mm, more preferably between 0.1 and 5 mm.
- Said inner layer may be made of an Ml material comprising a mass content of nickel of at least 30%.
- the material M1 comprises at least 40% by weight of nickel based on the total weight of the material Ml.
- the material M1 comprises at least 45% by weight of nickel, more preferably at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel based on the total weight of the material Ml.
- the material M1 can also comprise chromium in a content of less than 35% by weight based on the total weight of the material Ml, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight. weight, in particular less than 10% by weight, more particularly less than 5% by weight based on the total weight of the material Ml.
- the material M1 can also comprise molybdenum in a content of less than 35% by weight based on the total weight of the material Ml, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by weight based on the total weight of the material Ml.
- the material M1 comprises at least 40% by weight of nickel based on the total weight of the material Ml, preferably at least 45% by weight of nickel, more preferably at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel based on the total weight of the material Ml ; and less than 35% by weight of chromium, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5 % by weight of chromium based on the total weight of the material Ml; and less than 35% by weight of molybdenum, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5 % by weight of chromium based on the total weight of the material Ml; and less than 35% by weight of
- the material M1 can also comprise cobalt in a content of less than 10% by weight based on the total weight of the material Ml, advantageously less than 8% by weight, preferably less than 6% by weight, more preferably less than 4% by weight. weight, in particular less than 3% by weight, more particularly less than 2% by weight based on the total weight of the material Ml.
- the material M1 can also comprise tungsten in a content of less than 10% by weight based on the total weight of the material Ml, advantageously less than 9% by weight, preferably less than 8% by weight, more preferably less than 7% by weight. weight, in particular less than 6% by weight, more particularly less than 5% by weight based on the total weight of the material Ml.
- the material M1 can also comprise iron in a content of less than 25% by weight based on the total weight of the material Ml, advantageously less than 20% by weight, preferably less than 15% by weight, more preferably less than 10% by weight. weight, in particular less than 7% by weight, more particularly less than 5% by weight based on the total weight of the material Ml.
- the material M1 can also comprise manganese in a content of less than 5% by weight based on the total weight of the alloy, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1% by weight, more particularly less than 0.5% by weight based on the total weight of the material Ml.
- the material M1 can also comprise copper in a content of less than 50% by weight, advantageously less than 45% by weight, preferably less than 40% by weight, more preferably less than 35% by weight, particular less than 30% by weight, more particularly less than 25% by weight of copper based on the total weight of the material Ml.
- said intermediate layer has a thickness of between 0.1 and 50 mm.
- said intermediate layer can have a thickness of between 0.5 and 40 mm, preferably between 1 and 30 mm, more preferably between 1 and 25 mm.
- said intermediate layer 22 is disposed between said inner layer 21, in contact with the reagents, and said insulating layer 23 ( Figure 4). Said intermediate layer 22 can be made of a material M.
- the material M1 ' comprises at least 70% by weight of iron, advantageously at least 75% by weight, preferably at least 80% by weight, more preferably at least 85% by weight, in particular at minus 90% by weight, more particularly at least 95% by weight of iron based on the total weight of the material M.
- the material M1 ′ can also comprise less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0.5% by weight, more particularly less than 0.2% by weight, preferably less than 0.1% by weight based on the total weight of the material M.
- the material M1 ′ can comprise between 0.01 and 0.2% by weight of carbon based on the total weight of the material M.
- the material M1 ′ can also comprise less than 2% by weight of molybdenum, advantageously less than 1.5% by weight, preferably less than 1.25% by weight, more preferably less than 1% by weight of molybdenum based on the total weight of material M.
- the material M1 ′ can comprise between 0.1 and 1% by weight of molybdenum based on the total weight of the material M.
- the material M1 ′ can also comprise less than 5% by weight of chromium, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1% by weight.
- the material M1 'can comprise between 0.5 and 2% by weight of chromium based on the total weight of the material M.
- the material M1 ′ can also comprise less than 2% by weight of silicon, advantageously less than 1.5% by weight, preferably less than 1.25% by weight, more preferably less than 1% by weight of silicon based on total weight of material M. More particularly, the material M1 'can comprise between 0.1 and 1.5% by weight of silicon based on the total weight of the material M.
- the material M1 ′ can also comprise less than 2% by weight of manganese, advantageously less than 1.5% by weight, preferably less than 1.25% by weight, more preferably less than 1% by weight of manganese based on the total weight of the material Ml '. More particularly, the material Ml ′ can comprise between 0.1 and 1% by weight of manganese based on the total weight of the material
- said insulating layer is made of an M2 heat-insulating material.
- Said M2 heat-insulating material is selected from the group consisting of rock wool, glass wool, silicate fibers, calcium-magnesium silicates, calcium silicates, microporous insulators, cellular glass, expanded perlite, vermiculite exfoliated.
- Silicate fibers include, for example, aluminosilicate fibers.
- the side walls of said reactor comprise an insulating layer made of an M2 heat-insulating material whose thickness varies between 1 mm and 500 mm, preferably between 5 mm and 400 mm.
- the pressure at the inlet of said reactor is atmospheric pressure or a pressure greater than this, advantageously the pressure at the inlet of said reactor is greater than 1.5 bara, preferably greater than 2 , 0 bara, in particular greater than 2.5 bara, more particularly greater than 3.0 bara.
- step ii) is carried out at a pressure at the inlet of said reactor of between atmospheric pressure and 20 bara, preferably between 2 and 18 bara, more preferably between 3 and 15 bara.
- said at least one chlorinated compound and HF are brought into contact prior to the entry of these into said reactor.
- the resulting mixture is mixture C.
- said at least one chlorinated compound is in the liquid state. This is vaporized by mixing with HF. The resulting mixture C is then in gaseous form.
- the mixing between HF and said at least one chlorinated compound is carried out in a static mixer.
- said at least one chlorinated compound is introduced into the static mixer via one or more spray nozzles. Said at least one chlorinated compound is thus sprayed in the form of droplets before being vaporized by mixing with HF, thus forming a mixture C in gaseous form. Spraying said at least one chlorinated compound in the form of fine droplets makes it possible to ensure a more efficient vaporization of the latter.
- the average diameter of the droplets thus produced can be less than 500 ⁇ m.
- Said mixture C can optionally be heated or cooled before its introduction into said reactor. This step can be carried out via a heat exchanger to control the temperature at the inlet of said reactor.
- said stream B comprises 2-chloro-3,3,3-trifluoropropene, HF and HCl and optionally said at least one unreacted chlorine compound.
- Stream B can be purified, preferably by distillation, to isolate 2-chloro-3,3,3-trifluoropropene.
- the stream B comprises, in addition to 2-chloro-3,3,3-trifluoropropene, HCl, HF, 2,3,3,3-tetrafluoropropene.
- Stream B can optionally include 2,3-dichloro-3,3-difluoropropene, 2,3,3-trichloro-3-fluoropropene and / or 1,1,2,2,2-pentafluoropropane.
- stream B is purified, preferably by distillation, to form a first stream comprising 2,3,3,3-tetrafluoropropene, HCl and optionally 1,1,1,2,2-pentafluoropropane, and a second stream comprising HF and 2-chloro-3,3,3-trifluoropropene and optionally 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene.
- the distillation can be carried out at a pressure of 1 to 20 bara, preferably from 2 to 18 bara, more particularly at a pressure of 3 to 15 bara.
- the temperature at the top of the distillation column is from -85 ° C to -10 ° C, preferably from -60 ° C to -20 ° C.
- stream B is purified, preferably by distillation, to form a stream comprising HCl, 2-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and optionally 1,1,1,2 , 2-pentafluoropropane and a current comprising HF and optionally 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene.
- the stream comprising hydrofluoric acid and optionally 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene can be recycled to step ii) of the present process.
- said stream B obtained in step ii) is cooled prior to the purification mentioned above.
- said stream B obtained in step ii) is cooled to a temperature below 100 ° C., then distilled to form said first stream comprising 2,3,3,3-tetrafluoropropene, HCl and optionally 1,1,1 , 2,2-pentafluoropropane, and said second stream comprising HF and 2-chloro-3,3,3-trifluoropropene and optionally 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene ; the temperature at the top of the distillation column is from -60 ° C to -20 ° C and the distillation is carried out at a pressure of 3 to 15 bara.
- Said stream B can be cooled, before distillation, to a temperature below 95 ° C, advantageously below 90 ° C, preferably below 85 ° C, more preferably less than 80 ° C, in particular less than 70 ° C, more particularly less than 60 ° C, preferably less than 55 ° C, advantageously less than 50 ° C, preferably less than 40 ° C , more preferably preferably less than 30 ° C, particularly preferably less than 25 ° C, more particularly preferred less than 20 ° C. Cooling the product stream to such temperatures can facilitate subsequent distillation.
- the cooling of said stream B can be carried out by means of one or a plurality of heat exchangers.
- the cooling of said stream B can be carried out by passing it through one, two, three, four, five, six, seven, eight, nine or ten heat exchangers, preferably the number of heat exchangers is between 2 and 8, in particular between 3 and 7.
- Said second stream comprising HF and 2-chloro-3,3,3-trifluoropropene and optionally 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene can be purified, preferably by distillation , to form a third stream comprising hydrofluoric acid and optionally 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene, and a fourth stream comprising at least 95% by weight of 2 -chloro-3,3,3-trifluoropropene, preferably at least 98% by weight of 2-chloro-3,3,3-trifluoropropene based on the total weight of said fourth stream.
- the third stream comprising hydrofluoric acid and optionally 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene can be recycled in step ii) of the present process.
- said third stream is mixed with hydrofluoric acid before being used in step ii) of the present process.
- the method according to the present invention is carried out continuously.
- the process is carried out continuously and in the gas phase.
- said current A has an electrical conductivity of less than 15 mS / cm.
- the electrical conductivity of said current A is less than 14 mS / cm, preferably less than 13 mS / cm, more preferably less than 12 mS / cm, in particular less than 11 mS / cm, more particularly less than 10 mS / cm , preferably less than 9 mS / cm, advantageously less than 8 mS / cm, preferably less than 7 mS / cm, more preferably less than 6 mS / cm, particularly preferably less at 5 mS / cm.
- step ii) is carried out in the presence of hydrofluoric acid having an electrical conductivity of less than 10 mS / cm, preferably less than 5 mS / cm.
- the electrical conductivity of the third current that can be recycled to step ii) is less than 15 mS / cm, advantageously less than 10 mS / cm, preferably less than 5 mS / cm.
- the electrical conductivity of said current A or of HF or of the third current or of the current comprising HF in the embodiment described above is measured before step i) or ii).
- the electrical conductivity is measured when the current considered or the HF is in liquid form.
- Said method according to the present invention can therefore comprise a step of heating the current under consideration or of the HF prior to the implementation of step i) to supply said current A in gaseous form.
- said current A used in step i) is in gaseous form when it is brought into contact with HF.
- the electrical conductivity is measured at room temperature.
- the electrical conductivity is measured using an inductive conductivity measuring cell and according to the practice known to those skilled in the art.
- the measuring cell is coated with a material resistant to a corrosive medium, in particular resistant to hydrofluoric acid.
- the electrical conductivity of a current can be reduced to reach a conductivity of less than 15 ms / cm by reducing the concentration of electrolyte possibly present in it according to techniques known to those skilled in the art (distillation, cooling and decantation, passage on molecular sieves of 3 to 5 A or zeolites).
- Such an electrical conductivity makes it possible to improve the conversion and / or the selectivity of the reaction.
- an adiabatic reactor 1 is provided.
- said reactor 1 comprises a bottom 4, a cover 2 and side walls 3 forming a junction between the bottom 4 and the cover 2, at least one fixed bed 5 and at least one rod 6 supporting one or more temperature sensors 7a , 7b ( Figure 1).
- said bottom 4, said cover 2 and said side walls 3 each comprise at least one interior layer 21, an intermediate layer 22 disposed on said interior layer and an insulating layer 23 disposed around said intermediate layer 22.
- Said interior layers 21 , intermediate 22 and insulating 23 are made respectively of a material Ml, M and M2 as described above.
- said insulating layer 23 can be covered by a base layer 24.
- said insulating layer 23 is disposed between said intermediate layer 22 and said base layer 24 ( Figure 4).
- Said base layer 24 can be made of an M3 material.
- Said M3 material can be a metallic coating made with sheets aluminum, stainless steel or galvanized steel.
- said base layer has a thickness of between 0.2 mm and 2 mm.
- Said inner layer 21, said intermediate layer 22, said insulating layer 23 and said base layer 22 can be arranged one on the other according to techniques well known to those skilled in the art.
- the length of said at least one rod 6 is at least equal to the height of said fixed bed 5.
- said at least one rod 6 comprises at least one sensor or at least two sensors or at least 3 temperature sensors , advantageously at least 5 temperature sensors, preferably at least 7 temperature sensors, in particular at least 10 temperature sensors, preferably at least 12 temperature sensors, preferably at least 15 temperature sensors.
- At least one of said one or more temperature sensors, supported by said at least one rod is arranged in said fixed bed 5.
- at least two or three or four or five or six or seven temperature sensors, supported by said at least one rod are arranged in said fixed bed 5
- each rod 6 can comprise either an identical number or a different number of temperature sensors.
- each rod can include a temperature sensor in the sky and / or in the bottom of the reactor ( Figure 1, Reference 7b and 7b ').
- the temperature sensors 7a, 7b can be distributed equidistantly or in a more targeted manner according to the needs for controlling the temperature profile in the fixed bed.
- said reactor can comprise at least two canes 6, more preferably at least three canes 6, in particular at least four canes 6.
- said reactor can comprise between 1 and 20 canes 6, advantageously between 2 and 15 canes 6 , preferably between 3 and 10 rods 6.
- the reactor 1 is supplied with hydrocarbon compound 14 by supply lines 13.
- the reactor also comprises effluent or outlet lines 15 making it possible to evacuate the reaction mixture 16 from the reactor ( Figure 1).
- the feed or outlet lines of the reactor are made of material capable of also resisting corrosion, for example made of Ml material covered with a layer of M2 material and with a base layer made of a material M3.
- the supply lines can be tubular.
- the supply or outlet lines may include an inner layer, preferably made of an Ml material such as described above, an insulating layer, preferably made of a material M2 as described above, and a base layer, preferably made of a material M3 as described above.
- the reactor also includes one or more dephlegmator (s), one or more dip tube (s), one or more raw material introduction device (s), one or more support and retaining grid (s) of the catalyst.
- Said one or more dephlegmator (s) and / or said one or more dip tube (s) and / or said one or more device (s) for introducing the raw materials and / or said one or more grid (s) ) for supporting and retaining the catalyst may comprise an inner layer, preferably made of a material M1 as described above.
- the fixed bed 5 comprises a catalyst or an inert solid or both.
- the inert solid can be corundum, silicon carbide, quartz balls or rings, a metal lining with a metal M1 as defined in the present application or nickel balls.
- the fixed bed 5 comprises a catalyst
- the inert solid is placed in the upper part 17 and the lower part 18 of the fixed bed 5, said catalyst 19c being located between the layers of the inert solid 19a and 19b, in the part central 20 of the fixed bed 5.
- the fixed bed 5 comprises a catalyst
- the inert solid is placed in the upper part 17 or in the lower part 18 of the fixed bed 5.
- the fixed bed 5 comprises a catalyst
- no layer of inert solid is placed in the fixed bed.
- the lower part 18, the central part 20 and the upper part 17 of the fixed bed 5 can contain only inert solid.
- This alternative embodiment can be implemented when, for example, step ii) of the process according to the present invention is carried out in the absence of catalyst.
- the inert solid makes it possible to improve the distribution of the gases inside the reactor.
- the inert solid is corundum or nickel beads.
- the fixed bed 5 contains a layer of catalyst 19c in its central part 20.
- the catalyst is distributed homogeneously in the fixed bed.
- the homogeneous distribution of the catalyst in the fixed bed makes it possible to minimize disturbances in the flow of gases and to avoid hot spots within the catalyst layer. The presence of hot spots can lead to irreversible crystallization of the catalyst, resulting in deactivation of the latter.
- the fixed bed is loaded using the specific method of dense catalyst loading. This method is known to those skilled in the art. It allows to obtain an optimal distribution of the catalyst inside the reactor avoiding channeling during the reaction and attrition of the catalyst.
- the apparent mass density of the catalyst in the fixed bed is greater than the theoretical mass density of the latter. The apparent mass density is determined according to standard ASTM D1895.
- said reactor is a gas phase fluorination reactor.
- the present invention makes it possible to implement a process for the production of 2-chloro-3,3,3-trifluoropropene with a greater quantity of catalyst, if the latter is carried out in the presence of catalyst.
- controlling and controlling the temperature radially and longitudinally makes it possible to maintain a conversion and a selectivity of the reactions.
- an installation for manufacturing 2-chloro-3,3,3-trifluoropropene comprises an adiabatic reactor 101 according to the present invention, a reaction flow supply system for said reactor, a system for collecting and purifying the output flow 105 from said reactor.
- said installation also comprises at least one conductivity meter 121 capable of measuring the electrical conductivity of the reaction flow entering said reactor.
- said installation also comprises a heat exchanger 106 supplied by the outlet stream 105 and connected to a first distillation column 108.
- said installation also comprises a compressor 110 supplied with the current coming from said first distillation column 108.
- said installation comprises a second distillation column 112 supplied with a stream from the compressor 110. Said second distillation column 112 aims to remove all or part of the HCl present in the stream supplied to it.
- Said installation may also include a plurality of other distillation columns for purifying the 2,3,3,3-tetrafluoropropene if it is present in the outlet stream 105.
- the reaction flow supply system for reactor 101 comprises a supply line for hydrofluoric acid 102,120 and a supply line for said compound chlorine 103 and a device 104 for mixing hydrofluoric acid and said chlorine compound.
- Said mixing device 104 is preferably a static mixer.
- hydrofluoric acid and said chlorinated compound are mixed, sprayed and vaporized in said mixing device 104 before being introduced into said reactor 101.
- the outlet flow 105 from reactor 101 comprises 2-chloro-3, 3,3-trifluoropropene, HF, HCl, 2, 3, 3, 3- tetrafluoropropene and optionally said unreacted chlorine compound, 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene.
- the installation includes a heat exchanger 106 capable of cooling the outlet flow 105 from said reactor 101 to form a cooled current.
- the outlet stream 105 is routed to a cooling device 106.
- the outlet stream 105 is thus cooled to a temperature of 0 ° C to 70 ° C before being introduced into a distillation column 108 via a pipe 107.
- the distillation column 108 is configured so as to allow separation between hydrochloric acid and 2,3,3,3-tetrafluoropropene on the one hand and hydrofluoric acid and 2-chloro-3,3 on the other hand , 3-trifluoropropene and optionally said unreacted chlorine compound, 2,3-dichloro-3,3-difluoropropene and
- the stream comprising 2,3,3,3-tetrafluoropropene and hydrochloric acid is recovered at the top of distillation column 108 to be conveyed by a line 109 to a compressor 110.
- the compressor makes it possible to compress the stream comprising 2, 3,3,3-tetrafluoropropene and hydrochloric acid at a pressure between 10 and 25 bara.
- the current thus compressed is conveyed through line 111 to a second distillation column 112. This is configured so as to separate on one side the
- the hydrochloric acid is recovered and is at the head of the distillation column 112 to be conveyed to a purification device 116 via line 115.
- the hydrochloric acid purification device 116 is a device known from the prior art, for example from WO 2015/079137.
- the 2,3,3,3-tetrafluoropropene is recovered at the bottom of the distillation column 112 to be conveyed via line 113 to a purification device 114.
- the stream comprising HF and 2-chloro-
- 3.3-difluoropropene and 2,3,3-trichloro-3-fluoropropene is recovered at the bottom of distillation column 108.
- This stream can be conveyed to a fluorination reactor or purified.
- FIG. 5 represents an embodiment in which this current is purified. This is therefore routed via line 117 to a distillation column 118.
- the stream 119 obtained and recovered at the top of the distillation column comprises 2-chloro-3,3,3-trifluoropropene.
- the stream recovered at the bottom of distillation column 118 comprises HF and optionally said unreacted chlorine compound, 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene, is recycled to the mixing device 104.
- the electrical conductivity of the current thus recycled is measured by the conductimeter 12 before introducing it into the mixing device 104.
- the installation may also include a conductimeter 121 "and 12" to measure the electrical conductivity respectively of the HF from the supply line 102 and of the chlorine compound from the supply line 103, before the introduction of these into the mixing device 104.
- the stream recovered at the bottom of the distillation column 118 and comprising HF and optionally said chlorine compound n '' unreacted, 2,3-dichloro-3,3-difluoropropene and 2,3,3-trichloro-3-fluoropropene, can be recycled to reactor 101.
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1855106A FR3082204B1 (en) | 2018-06-12 | 2018-06-12 | 2-CHLORO-3,3,3-TRIFLUOROPROPENE PRODUCTION PROCESS AND PLANT FOR IMPLEMENTING THE SAME. |
PCT/FR2019/051354 WO2019239038A1 (en) | 2018-06-12 | 2019-06-06 | Method for producing 2-chloro-3,3,3-trifluoropropene and facility for implementing same |
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EP3807240A1 true EP3807240A1 (en) | 2021-04-21 |
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Application Number | Title | Priority Date | Filing Date |
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EP19745192.5A Pending EP3807240A1 (en) | 2018-06-12 | 2019-06-06 | Method for producing 2-chloro-3,3,3-trifluoropropene and facility for implementing same |
Country Status (5)
Country | Link |
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US (1) | US11192839B2 (en) |
EP (1) | EP3807240A1 (en) |
CN (1) | CN112262117A (en) |
FR (1) | FR3082204B1 (en) |
WO (1) | WO2019239038A1 (en) |
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US8058486B2 (en) | 2004-04-29 | 2011-11-15 | Honeywell International Inc. | Integrated process to produce 2,3,3,3-tetrafluoropropene |
CN101528645B (en) | 2006-10-31 | 2013-10-30 | 纳幕尔杜邦公司 | Processes for production of fluoropropanes and halopropenes and azeotropic compositions of 2-chloro-3,3,3-trifluoro-1-propene with HF and of 1,1,1,2,2-pentafluoropropane with HF |
US7795480B2 (en) * | 2007-07-25 | 2010-09-14 | Honeywell International Inc. | Method for producing 2-chloro-3,3,3,-trifluoropropene (HCFC-1233xf) |
KR20120093202A (en) * | 2009-10-09 | 2012-08-22 | 다우 글로벌 테크놀로지스 엘엘씨 | Adiabatic plug flow reactors and process for producing a chlorinated and/or fluorinated propene and higher alkene |
US9120716B2 (en) * | 2010-10-22 | 2015-09-01 | Arkema France | Process for the preparation of 2,3,3,3 tetrafluoropropene |
CN103998405B (en) * | 2011-12-14 | 2016-06-08 | 阿克马法国公司 | The preparation method of 2,3,3,3-tetrafluoropropene |
EP2882704B1 (en) * | 2012-08-08 | 2018-02-28 | Daikin Industries, Ltd. | Process for producing 2,3,3,3-tetrafluoropropene |
FR3013606B1 (en) | 2013-11-28 | 2015-11-13 | Arkema France | PROCESS FOR PURIFYING HYDROCHLORIC ACID |
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2018
- 2018-06-12 FR FR1855106A patent/FR3082204B1/en active Active
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- 2019-06-06 CN CN201980038986.2A patent/CN112262117A/en active Pending
- 2019-06-06 WO PCT/FR2019/051354 patent/WO2019239038A1/en unknown
- 2019-06-06 US US16/973,192 patent/US11192839B2/en active Active
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US20210261486A1 (en) | 2021-08-26 |
FR3082204B1 (en) | 2020-08-14 |
FR3082204A1 (en) | 2019-12-13 |
US11192839B2 (en) | 2021-12-07 |
WO2019239038A1 (en) | 2019-12-19 |
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