WO2008030443A1 - Catalytic isomerization processes of 1,3,3,3-tetrafluoropropene for making 2,3,3,3-tetrafluoropropene - Google Patents
Catalytic isomerization processes of 1,3,3,3-tetrafluoropropene for making 2,3,3,3-tetrafluoropropene Download PDFInfo
- Publication number
- WO2008030443A1 WO2008030443A1 PCT/US2007/019318 US2007019318W WO2008030443A1 WO 2008030443 A1 WO2008030443 A1 WO 2008030443A1 US 2007019318 W US2007019318 W US 2007019318W WO 2008030443 A1 WO2008030443 A1 WO 2008030443A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hfc
- catalyst
- tetrafluoropropene
- chromium
- transition metal
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 title claims description 5
- 238000006317 isomerization reaction Methods 0.000 title abstract description 8
- 230000003197 catalytic effect Effects 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 24
- QCMJBECJXQJLIL-UHFFFAOYSA-L chromium(6+);oxygen(2-);difluoride Chemical group [O-2].[O-2].[F-].[F-].[Cr+6] QCMJBECJXQJLIL-UHFFFAOYSA-L 0.000 claims description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- -1 transition metal modified chromium oxide Chemical class 0.000 claims description 18
- 150000003624 transition metals Chemical class 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- BSKAIKMQTLKUOW-UHFFFAOYSA-N chromium;fluoro hypofluorite Chemical class [Cr].FOF BSKAIKMQTLKUOW-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
Definitions
- the present disclosure relates in general to the processes of catalyzed isomerization of 1 ,3,3,3-tetrafluoropropene (HFC-1234ze) to make 2,3,3,3-tetrafluoropropene (HFC-1234yf).
- HFC-1234ze 1 ,3,3,3-tetrafluoropropene
- HFC-1234yf 2,3,3,3-tetrafluoropropene
- Tetrafluoropropenes having zero ozone depletion and low global warming potential, have been identified as potential refrigerants. .
- the toxicity, boiling point, and other physical properties in this class of chemicals varies greatly from isomer to isomer.
- One tetrafluoropropenes having valuable properties is 2,3,3,3 tetrafluoropropene (HFC-1234ye).
- HFC-1234ye 2,3,3,3 tetrafluoropropene
- the present disclosure provides a process of catalyzed isomerization of HFC-1234ze to make HFC-1234yf.
- the process comprises contacting HFC-1234ze with a suitable catalyst in a reactor to obtain a product mixture comprising HFC-1234yf.
- the present disclosure is to a new manufacturing process for the production of 2,3,3,3-tetrafluoropropene.
- the process includes the step of contacting 1 ,3,3,3-tetrafluoropropene with a catalyst in a reactor to obtain a product mixture comprising 2,3,3,3-tetrafluoropropene
- HFC-1234ze may exist as one of two configurational isomers, E or Z.
- HFC-1234ze as used herein refers to the isomers, E-HFC-1234ze or Z- HFC-1234ze, as well as any combinations or mixtures of such isomers.
- amorphous is intended to mean that there is no substantial peak in a X-ray diffraction pattern of the subject solid.
- the suitable catalyst contains chromium.
- suitable catalysts include chromium oxyfluoride.
- the chromium oxyfluoride catalysts can be made by treating CT 2 O 3 (chromium oxide) with a source of fluorine such as HF, CCI3F or hydrofluorocarbons.
- a chromium oxyfluoride catalyst is made by treating dry Cr 2 O 3 with a fluorination agent such as CCI3F or HF.
- This treatment can be accomplished by placing the CT2O3 in a suitable container (which can be the reactor to be used to perform the dehydrofluorination reaction) and thereafter passing HF over the dry Cr2 ⁇ 3 for a suitable period of time (e.g., about 15 to 300 minutes) at a suitable temperature (e.g., about 200 0 C to 45O 0 C), such as what described in Example 1.
- a suitable container which can be the reactor to be used to perform the dehydrofluorination reaction
- HF e.g., about 15 to 300 minutes
- a suitable temperature e.g., about 200 0 C to 45O 0 C
- a chromium oxyfluoride catalyst is made by treating Cr 2 O 3 with a hydrofluorocarbon at an elevated temperature.
- a chromium oxyfluoride catalyst is made in situ.
- the reactant HFC-£-1234ze can be employed in the formation of a chromium oxyfluoride catalyst by heating together with Cr 2 O 3 in the reactor.
- Cr 2 Oa is commercially available from Engelhard Corporation (101 Wood Avenue, P.O. Box 770, Iselin, NJ 08830-0770).
- Cr 2 ⁇ 3 can also be prepared by pyrolysis of ammonium dichromate as disclosed in U.S. Patent No. US 5,036,036, which is incorporated herein by reference.
- Cr 2 O 3 can also be prepared by the reaction of chromium (Vl) oxide with a reducing solvent, such as methanol, as disclosed in U.S. Patent No. US 4,828,818, which is incorporated herein by reference.
- a reducing solvent such as methanol
- Cr 2 O 3 can also be prepared by reducing chromium (Vl) oxide in water with a suitable reducing agent, such as ethanol, as disclosed in U.S. Patent No. US 3,258,500, which is incorporated herein by reference.
- a suitable reducing agent such as ethanol
- the amount of potassium and other alkali metals in Cr 2 O 3 can be reduced by a water washing step as disclosed in U.S. Patent No. US 5,036,036.
- the chromium oxyfluoride catalyst has surface areas of about 20 m 2 /g to about 500 m 2 /g.
- the chromium oxyfluoride catalyst has surface areas of about 40 m 2 /g to about 350 m 2 /g. In another embodiment of this invention, the chromium oxyfluoride catalyst has surface areas of about 60 m 2 /g to about 300 m 2 /g.
- the chromium oxyfluoride catalyst has surface areas of about 100 m 2 /g to about 300 m 2 /g.
- the chromium oxyfluoride catalyst contains an alkali metal content of about 2000 ppm or less.
- the chromium oxyfluoride catalyst contains an alkali metal content of about 300 ppm or less.
- the chromium oxyfluoride catalyst contains an alkali metal content of about 100 ppm or less. In one embodiment of this invention, the chromium oxyfluoride catalyst is amorphous.
- the chromium oxyfluoride catalyst is prepared from crystalline Ci-Cr 2 O 3 .
- suitable catalysts include transition metal modified chromium oxides and transition metal modified chromium oxyfluorides.
- transition metals include magnesium (e.g. magnesium fluoride), Group VIIB metals (e.g., manganese), Group IMB metals (e.g., lanthanum), and zinc.
- transition metals are normally present as halides (e.g., fluorides), as oxides and/or as oxyhalides.
- these transition metals are supported on chromium oxides or chromium oxyfluorides.
- catalysts which may be used for the isomerization contain aluminum.
- Such catalysts include fluorided alumina, aluminum fluoride.
- Such catalysts also include transition metal modified alumina, transition metal modified fluorided alumina and transition metal modified aluminum fluoride.
- Such transition metals include magnesium (e.g. magnesium fluoride), Group VIIB metals (e.g., manganese), Group IMB metals (e.g., lanthanum), and zinc.
- transition metals are normally present as halides (e.g., fluorides), as oxides and/or as oxyhalides.
- these transition metals are supported on alumina, fluorided alumina or aluminum fluoride. .
- Fluorided alumina and aluminum fluoride can be prepared as described in U.S. Pat. No. 4,902,838, herein incorporated by reference.
- the contact time of HFC-1234ze with the chromium oxyfluoride catalyst can vary widely depending on the degree of conversion desired and generally will be from about 1 second to about 1000 seconds. In one embodiment of the invention, the contact time ranges from about 10 seconds to about 200 seconds.
- the temperature employed in the isomerization processes typically ranges from about 200° C to 500° C. In one embodiment of the invention, the temperature employed in the isomerization processes ranges from about 300° C to 400° C.
- the reaction pressure for the processes above can be subatmospheric, atmospheric or superatmosphehc. In one embodiment of the invention, the reaction pressure is near atmospheric.
- the reactions in the processes above can be done in the presence of oxygen.
- the reactions in the processes above is done in the presence of air.
- air is co-fed with the reactant into the reactor.
- the reactions in the processes above can be done in the presence of inert gases such as nitrogen, helium, argon, or their mixtures thereof.
- inert gases such as nitrogen, helium, argon, or their mixtures thereof.
- the inert gas is co-fed with the reactant into the reactor.
- the inert gas is nitrogen.
- HFC-1234yf present in the product mixture may be separated from the other components of the product mixture and unreacted starting materials by fractional distillation.
- HF is added to the product mixture, and separation of HFC-1234yf includes isolation of azeotrope or near azeotrope of HFC-1234yf and HF and further processing to produce HF-free HFC-1234yf by using procedures similar to that disclosed in US Patent Publication US 2006/0106263 A1 , herein incorporated by reference.
- Unreacted HFC-1234ze can be separated and recycled to the reactor for the production of additional HFC-1234yf.
- unreacted HFC-1234ze present in the product mixture may be separated from the other components of the product mixture by fractional distillation.
- HF is added to the product mixture, and separation of unreacted HFC-1234ze includes isolation of azeotrope or near azeotrope of HFC-1234ze and HF and further processing to produce HF-free HFC-1234ze by using procedures similar to that disclosed in US Patent Publication US 2006/0106263 A1.
- U.S. Application No. 60/732397 discloses an azeotrope or near- azeotrope composition of the E- isomer of HFC-1234ze and HF.
- U.S. Application No. 60/816650 discloses an azeotrope or near-azeotrope composition of the Z- isomer of HFC-1234ze and HF.
- the reactors, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the processes of embodiments of this invention should be constructed of materials resistant to corrosion.
- Typical materials of construction include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as MonelTM nickel-copper alloys, HastelloyTM nickel-based alloys and, InconelTM nickel-chromium alloys, and copper-clad steel.
- Chromium oxide used in this example was synthesized according to the process desribed in US Patent Number US3,258,500 from the reduction of chromium trioxide. This form of chromium oxide is usually amorphous and has a surface area in excess of 180 m 2 /gm.
- An lnconel tube (5/8 inch OD) was filled with 6 cc (7.12 gm) of chromium oxide gel pellets, crushed and sieved to 12/20 mesh.
- the catalyst was heated to 200° C for 15 minutes under a purge of N 2 (50 seem, 8.33 x 10 "7 m 3 /s). Then the temperature was raised to 325° C for 10 minutes, to 400° C for 20 minutes, and lowered to 300° C for 35 minutes. The temperature was raised to 325° C for 60 minutes while flowing N 2 (35 seem, 5.83 x 10 "7 m 3 /s) and HF (12 seem, 2.00 x 10 "7 m 3 /s) for 35 minutes.
- the temperature was raised to 350° C for 60 minutes, 375° C for 90 minutes, 400° C for 30 minutes, and 425° C for 40 minutes.
- the flow of N 2 was reduced to 25 seem (4.17 x 10 "7 m 3 /s) and HF raised to 20 seem (3.33 x 10 "7 m 3 /s) for 20 minutes.
- the flow of N 2 was reduced to 15 seem (2.50 x 10 "7 m 3 /s) and HF raised to 28 seem (4.67 x 10 "7 m 3 /s) for 20 minutes.
- the temperature of the catalyst bed was set to 350° C and E-HFC- 1234ze (E-1 ,3,3,3-tetrafluoropropene) was flowed through the reactor at 6 seem (1.00 x 10 '7 m 3 /s).
- the product mixture effluent was analyzed by both GC-MS and NMR and found to have the following composition: (analytical results were given in units of GC area%) 31.1 % Z-HFC- 1234ze, 59.9 % E-HFC-1234ze, 1.3 % 236fa, 3.8 % 245fa, and 3.9 % HFC-1234yf.
- Example 2 This example is prophetic. All the other conditions are the same as in Example 1.
- the temperature of the catalyst bed is set to 400° C and E- HFC-1234ze is flowed through the reactor at 6 seem (1.00 x 10 "7 m 3 /s).
- the product mixture effluent is analyzed by both GC-MS and NMR and found to have the following composition: (analytical results were given in units of GC area%) 35% Z-HFC-1234ze, 40% E-HFC-1234ze, 2% 236fa, 5% 245fa, and 18% HFC-1234yf.
- Example 1 This example is prophetic. All the other conditions are the same as in Example 1.
- the temperature of the catalyst bed is set to 350° C and E-HFC- 1234ze is flowed through the reactor at 3 seem (2.00 x 10 ⁇ 8 m 3 /s), thereby doubling the contact time compared to Example 1.
- the product mixture effluent is analyzed by both GC-MS and NMR and found to have the following composition: (analytical results were given in units of GC area%) 37% Z-HFC-1234ze, 35% E-HFC-1234ze, 3% 236fa, 5% 245fa, and 20% HFC-1234yf.
- a catalyst of higher surface area is used as described in US Patent Number US4,828,818.
- This is an aerogel catalyst with a high surface area, typically greater than 400 m 2 /gm.
- An inconel tube (5/8 inch OD) is filled with 6 cc (0.38 gm) of chromium oxide gel particles, crushed and sieved to 12/20 mesh.
- the catalyst is heated to 200° C for 15 minutes under a purge of N 2 (50 seem, 8.33 x 10 '7 m 3 /s). Then the temperature is raised to 325° C for 10 minutes, to 400° C for 20 minutes, and lowered to 300° C for 35 minutes.
- the temperature is raised to 325° C for 60 minutes while flowing N 2 (35 seem, 5.83 x 10 "7 m 3 /s) and HF (12 seem, 2.00 x 10 '7 m 3 /s) for 35 minutes. While maintaining this flow, the temperature is raised to 350° C for 60 minutes, 375° C for 90 minutes, 400° C for 30 minutes, and 425° C for 40 minutes.
- the flow of N 2 is reduced to 25 seem (4.17 x 10 ⁇ 7 m 3 /s) and HF raised to 20 seem (3.33 x 10 '7 m 3 /s) for 20 minutes.
- the temperature of the catalyst bed is set to 350° C and E-HFC- 1234ze is flowed through the reactor at 6 seem (1.00 x 10 '7 m 3 /s).
- the product mixture effluent is analyzed by both GC-MS and NMR and found to have the following composition: (analytical results were given in units of GC area%) 30% E-HFC-1234ze, 30% E-HFC-1234ze, 1.3% 236fa, 4.8% 245fa, and 33.9% HFC-1234yf.
- the higher surface area catalyst substantially increases the amount of the desired HFC-1234yf.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a process of catalyzed isomerization of HFC-1234ze to make HFC-1234yf. The process comprises contacting HFC-1234ze with a suitable catalyst in a reactor to obtain a product mixture comprising HFC-1234yf.
Description
TITLE
CATALYTIC ISOMERIZATION PROCESSES OF 1,3,3,3-
TETRAFLUOROPROPENE FOR MAKING 2,3,3,3-
TETRAFLUOROPROPENE
BACKGROUND OF THE INVENTION
Field of the Disclosure
The present disclosure relates in general to the processes of catalyzed isomerization of 1 ,3,3,3-tetrafluoropropene (HFC-1234ze) to make 2,3,3,3-tetrafluoropropene (HFC-1234yf). Description of Related Art
As a result of the Montreal Protocol phasing out ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), industry has been working for the past few decades to find replacement refrigerants. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new hydrofluorocarbon refrigerants, HFC-134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol. The production of other hydrofluorocarbons for use in applications such as solvents, blowing agents, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishants and power cycle working fluids has also been the subject of considerable interest.
There is also considerable interest in developing new refrigerants with reduced global warming potential for the mobile air-conditioning market.
Tetrafluoropropenes, having zero ozone depletion and low global warming potential, have been identified as potential refrigerants. . However, the toxicity, boiling point, and other physical properties in this class of chemicals varies greatly from isomer to isomer. One tetrafluoropropenes having valuable properties is 2,3,3,3 tetrafluoropropene (HFC-1234ye). Thus, there is a need for new manufacturing processes for the production of tetrafluoropropenes.
SUMMARY OF THE INVENTION
The present disclosure provides a process of catalyzed isomerization of HFC-1234ze to make HFC-1234yf. The process comprises contacting HFC-1234ze with a suitable catalyst in a reactor to obtain a product mixture comprising HFC-1234yf.
The present disclosure is to a new manufacturing process for the production of 2,3,3,3-tetrafluoropropene. The process includes the step of contacting 1 ,3,3,3-tetrafluoropropene with a catalyst in a reactor to obtain a product mixture comprising 2,3,3,3-tetrafluoropropene
The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
Before addressing details of embodiments described below, some terms are defined or clarified.
HFC-1234ze may exist as one of two configurational isomers, E or Z. HFC-1234ze as used herein refers to the isomers, E-HFC-1234ze or Z- HFC-1234ze, as well as any combinations or mixtures of such isomers.
The term "a chromium oxyfluoride catalyst" is intended to mean a chromium oxyfluoride represented by formula
wherein x + y/2 = 3.
The term "amorphous" is intended to mean that there is no substantial peak in a X-ray diffraction pattern of the subject solid. As used herein, the terms "comprises," "comprising," "includes,"
"including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the
following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
Also, use of "a" or "an" are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. A process has been provided to catalytically isomerize HFC-1234ze to form HFC-1234yf. The process comprises contacting HFC-1234ze with a suitable catalyst in a reactor to obtain a product mixture comprising HFC-1234yf.
In one embodiment of this invention, the suitable catalyst contains chromium. Such suitable catalysts include chromium oxyfluoride.
Many aspects and embodiments have been described in this disclosure and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.
Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.
The synthesis of HFC-1234ze is disclosed by Mukhopadhyay et al. in US Patent Publication Number 2005/0245773 A1 , which is incorporated herein by reference.
The chromium oxyfluoride catalysts can be made by treating CT2O3 (chromium oxide) with a source of fluorine such as HF, CCI3F or hydrofluorocarbons. In one embodiment of this invention, a chromium oxyfluoride catalyst is made by treating dry Cr2O3 with a fluorination agent such as CCI3F or HF. This treatment can be accomplished by placing the CT2O3 in a suitable container (which can be the reactor to be used to perform the dehydrofluorination reaction) and thereafter passing HF over the dry Cr2θ3 for a suitable period of time (e.g., about 15 to 300 minutes) at a suitable temperature (e.g., about 200 0C to 45O 0C), such as what described in Example 1.
In another embodiment of this invention, a chromium oxyfluoride catalyst is made by treating Cr2O3 with a hydrofluorocarbon at an elevated temperature.
In another embodiment of this invention, a chromium oxyfluoride catalyst is made in situ. For example, the reactant HFC-£-1234ze can be employed in the formation of a chromium oxyfluoride catalyst by heating together with Cr2O3 in the reactor.
Cr2Oa is commercially available from Engelhard Corporation (101 Wood Avenue, P.O. Box 770, Iselin, NJ 08830-0770).
Cr2θ3 can also be prepared by pyrolysis of ammonium dichromate as disclosed in U.S. Patent No. US 5,036,036, which is incorporated herein by reference.
Cr2O3 can also be prepared by the reaction of chromium (Vl) oxide with a reducing solvent, such as methanol, as disclosed in U.S. Patent No. US 4,828,818, which is incorporated herein by reference.
Cr2O3 can also be prepared by reducing chromium (Vl) oxide in water with a suitable reducing agent, such as ethanol, as disclosed in U.S. Patent No. US 3,258,500, which is incorporated herein by reference.
The amount of potassium and other alkali metals in Cr2O3 can be reduced by a water washing step as disclosed in U.S. Patent No. US 5,036,036.
In one embodiment of this invention, the chromium oxyfluoride catalyst has surface areas of about 20 m2/g to about 500 m2/g.
In another embodiment of this invention, the chromium oxyfluoride catalyst has surface areas of about 40 m2/g to about 350 m2/g. In another embodiment of this invention, the chromium oxyfluoride catalyst has surface areas of about 60 m2/g to about 300 m2/g.
In another embodiment of this invention, the chromium oxyfluoride catalyst has surface areas of about 100 m2/g to about 300 m2/g.
In one embodiment of this invention, the chromium oxyfluoride catalyst contains an alkali metal content of about 2000 ppm or less.
In another embodiment of this invention, the chromium oxyfluoride catalyst contains an alkali metal content of about 300 ppm or less.
In another embodiment of this invention, the chromium oxyfluoride catalyst contains an alkali metal content of about 100 ppm or less. In one embodiment of this invention, the chromium oxyfluoride catalyst is amorphous.
In another embodiment of this invention, the chromium oxyfluoride catalyst is prepared from crystalline Ci-Cr2O3.
In another embodiment of this invention, suitable catalysts include transition metal modified chromium oxides and transition metal modified chromium oxyfluorides. Such transition metals include magnesium (e.g. magnesium fluoride), Group VIIB metals (e.g., manganese), Group IMB metals (e.g., lanthanum), and zinc. In use, such transition metals are normally present as halides (e.g., fluorides), as oxides and/or as oxyhalides. Typically, these transition metals are supported on chromium oxides or chromium oxyfluorides.
In another embodiment of this invention, other suitable catalysts which may be used for the isomerization contain aluminum. Such catalysts include fluorided alumina, aluminum fluoride. Such catalysts also include transition metal modified alumina, transition metal modified fluorided alumina and transition metal modified aluminum fluoride. Such transition metals include magnesium (e.g. magnesium fluoride), Group VIIB metals (e.g., manganese), Group IMB metals (e.g., lanthanum), and zinc. In use, such transition metals are normally present as halides (e.g., fluorides), as
oxides and/or as oxyhalides. Typically, these transition metals are supported on alumina, fluorided alumina or aluminum fluoride. . Fluorided alumina and aluminum fluoride can be prepared as described in U.S. Pat. No. 4,902,838, herein incorporated by reference. The contact time of HFC-1234ze with the chromium oxyfluoride catalyst can vary widely depending on the degree of conversion desired and generally will be from about 1 second to about 1000 seconds. In one embodiment of the invention, the contact time ranges from about 10 seconds to about 200 seconds. The temperature employed in the isomerization processes typically ranges from about 200° C to 500° C. In one embodiment of the invention, the temperature employed in the isomerization processes ranges from about 300° C to 400° C.
The reaction pressure for the processes above can be subatmospheric, atmospheric or superatmosphehc. In one embodiment of the invention, the reaction pressure is near atmospheric.
Optionally, the reactions in the processes above can be done in the presence of oxygen. In one embodiment of the invention, the reactions in the processes above is done in the presence of air. In another embodiment of the invention, air is co-fed with the reactant into the reactor.
Optionally, the reactions in the processes above can be done in the presence of inert gases such as nitrogen, helium, argon, or their mixtures thereof. In one embodiment of the invention, the inert gas is co-fed with the reactant into the reactor. In another embodiment of the invention, the inert gas is nitrogen.
In one embodiment of this invention, HFC-1234yf present in the product mixture may be separated from the other components of the product mixture and unreacted starting materials by fractional distillation. In another embodiment of this invention, HF is added to the product mixture, and separation of HFC-1234yf includes isolation of azeotrope or near azeotrope of HFC-1234yf and HF and further processing to produce HF-free HFC-1234yf by using procedures similar to that disclosed in US
Patent Publication US 2006/0106263 A1 , herein incorporated by reference.
U.S. Application No. 60/732321 , filed on November 1, 2005 and incorporated herein by reference, discloses an azeotrope or near- azeotrope composition of HFC-1234yf and HF.
Unreacted HFC-1234ze can be separated and recycled to the reactor for the production of additional HFC-1234yf.
In one embodiment of this invention, unreacted HFC-1234ze present in the product mixture may be separated from the other components of the product mixture by fractional distillation.
In another embodiment of this invention, HF is added to the product mixture, and separation of unreacted HFC-1234ze includes isolation of azeotrope or near azeotrope of HFC-1234ze and HF and further processing to produce HF-free HFC-1234ze by using procedures similar to that disclosed in US Patent Publication US 2006/0106263 A1.
U.S. Application No. 60/732397, filed on November 1 , 2005 and incorporated herein by reference, discloses an azeotrope or near- azeotrope composition of the E- isomer of HFC-1234ze and HF. U.S. Application No. 60/816650, filed on June 27, 2006 and incorporated herein by reference, discloses an azeotrope or near-azeotrope composition of the Z- isomer of HFC-1234ze and HF.
The reactors, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the processes of embodiments of this invention should be constructed of materials resistant to corrosion. Typical materials of construction include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel.
EXAMPLES
The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.
LEGEND
1234ze is CF3CH=CHF 1234yf is CF3CF=CH2
EXAMPLE 1 Chromium oxide used in this example was synthesized according to the process desribed in US Patent Number US3,258,500 from the reduction of chromium trioxide. This form of chromium oxide is usually amorphous and has a surface area in excess of 180 m2/gm.
An lnconel tube (5/8 inch OD) was filled with 6 cc (7.12 gm) of chromium oxide gel pellets, crushed and sieved to 12/20 mesh. The catalyst was heated to 200° C for 15 minutes under a purge of N2 (50 seem, 8.33 x 10"7 m3/s). Then the temperature was raised to 325° C for 10 minutes, to 400° C for 20 minutes, and lowered to 300° C for 35 minutes. The temperature was raised to 325° C for 60 minutes while flowing N2 (35 seem, 5.83 x 10"7 m3/s) and HF (12 seem, 2.00 x 10"7 m3/s) for 35 minutes. While maintaining this flow, the temperature was raised to 350° C for 60 minutes, 375° C for 90 minutes, 400° C for 30 minutes, and 425° C for 40 minutes. The flow of N2 was reduced to 25 seem (4.17 x 10"7 m3/s) and HF raised to 20 seem (3.33 x 10"7 m3/s) for 20 minutes. Then the flow of N2 was reduced to 15 seem (2.50 x 10"7 m3/s) and HF raised to 28 seem (4.67 x 10"7 m3/s) for 20 minutes. Then the flow of N2 was reduced to 5 seem (8.33 x 10~8 m3/s) and HF raised to 36 seem (6.00 x 10"7 m3/s) for 20 minutes. Finally, the N2 was shut off and the HF flow was raised to 40 seem (6.67 x 10"7 m3/s) for 20 minutes and then the temperature was reduced to the reaction temperature.
The temperature of the catalyst bed was set to 350° C and E-HFC- 1234ze (E-1 ,3,3,3-tetrafluoropropene) was flowed through the reactor at 6 seem (1.00 x 10'7 m3/s). The product mixture effluent was analyzed by both GC-MS and NMR and found to have the following composition: (analytical results were given in units of GC area%) 31.1 % Z-HFC- 1234ze, 59.9 % E-HFC-1234ze, 1.3 % 236fa, 3.8 % 245fa, and 3.9 % HFC-1234yf.
EXAMPLE 2
This example is prophetic. All the other conditions are the same as in Example 1. The temperature of the catalyst bed is set to 400° C and E- HFC-1234ze is flowed through the reactor at 6 seem (1.00 x 10"7 m3/s). The product mixture effluent is analyzed by both GC-MS and NMR and found to have the following composition: (analytical results were given in units of GC area%) 35% Z-HFC-1234ze, 40% E-HFC-1234ze, 2% 236fa, 5% 245fa, and 18% HFC-1234yf.
EXAMPLE 3
This example is prophetic. All the other conditions are the same as in Example 1.
The temperature of the catalyst bed is set to 350° C and E-HFC- 1234ze is flowed through the reactor at 3 seem (2.00 x 10~8 m3/s), thereby doubling the contact time compared to Example 1. The product mixture effluent is analyzed by both GC-MS and NMR and found to have the following composition: (analytical results were given in units of GC area%) 37% Z-HFC-1234ze, 35% E-HFC-1234ze, 3% 236fa, 5% 245fa, and 20% HFC-1234yf.
EXAMPLE 4
This example is prophetic. In this example, a catalyst of higher surface area is used as described in US Patent Number US4,828,818. This is an aerogel catalyst with a high surface area, typically greater than 400 m2/gm. An inconel tube (5/8 inch OD) is filled with 6 cc (0.38 gm) of chromium oxide gel particles, crushed and sieved to 12/20 mesh. The catalyst is heated to 200° C for 15 minutes under a purge of N2 (50 seem, 8.33 x 10'7 m3/s). Then the temperature is raised to 325° C for 10 minutes, to 400° C for 20 minutes, and lowered to 300° C for 35 minutes. The temperature is raised to 325° C for 60 minutes while flowing N2 (35 seem, 5.83 x 10"7 m3/s) and HF (12 seem, 2.00 x 10'7 m3/s) for 35 minutes. While maintaining this flow, the temperature is raised to 350° C for 60 minutes, 375° C for 90 minutes, 400° C for 30 minutes, and 425° C for 40 minutes. The flow of N2 is reduced to 25 seem (4.17 x 10~7 m3/s) and HF
raised to 20 seem (3.33 x 10'7 m3/s) for 20 minutes. Then the flow of N2 is reduced to 15 seem (2.50 x 10"7 m3/s) and HF raised to 28 seem (4.67 x 10'7 m3/s) for 20 minutes. Then the flow of N2 is reduced to 5 seem (8.33 x 10'8 m3/s) and HF raised to 36 seem (6.00 x 10'7 m3/s) for 20 minutes. Finally, the N2 is shut off and the HF flow is raised to 40 seem (6.67 x 10"7 m3/s) for 20 minutes and then the temperature is reduced to the reaction temperature.
The temperature of the catalyst bed is set to 350° C and E-HFC- 1234ze is flowed through the reactor at 6 seem (1.00 x 10'7 m3/s). The product mixture effluent is analyzed by both GC-MS and NMR and found to have the following composition: (analytical results were given in units of GC area%) 30% E-HFC-1234ze, 30% E-HFC-1234ze, 1.3% 236fa, 4.8% 245fa, and 33.9% HFC-1234yf. The higher surface area catalyst substantially increases the amount of the desired HFC-1234yf.
Claims
1. A process comprising: contacting 1 ,3,3,3-tetrafluoropropene with a catalyst in a reactor to obtain a product mixture comprising
2,3,3,3-tetrafluoropropene.
2. The process of claim 1 wherein the catalyst contains chromium.
3. The process of claim 2 wherein the catalyst is a chromium oxyfluoride.
4. The process of claim 3 wherein said chromium oxyfluoride is made by reacting CT2O3 with a source of fluorine.
5. The process of claim 4 wherein said source of fluorine is selected from the group consisting of HF, CCI3F and hydrofluorocarbons.
6. The process of claim 2 wherein said catalyst is a transition metal modified chromium oxide or a transition metal modified chromium oxyfluoride.
7. The process of claim 6 wherein said transition metal is selected from the group consisting of magnesium, Group VIIB metals, Group HIB metals, and zinc. .
8. The process of claim 7 wherein said transition metal is supported on chromium oxide or chromium oxyfluoride.
9. The process of claim 1 wherein catalyst contains aluminum.
10. The process of claim 9 wherein said catalyst is fluorided alumina or aluminum fluoride.
11. The process of claim 9 wherein said catalyst is selected from the group consisting of transition metal modified alumina, transition metal modified fluorided alumina and transition metal modified aluminum fluoride.
12. The process of claim 11 wherein said transition metal is selected from the group consisting of magnesium, Group VIIB metals, Group IMB metals, and zinc.
13. The process of claim 12 wherein said transition metal is supported on alumina, fluorided alumina or aluminum fluoride. .
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200780041195.2A CN101535228B (en) | 2006-09-05 | 2007-09-05 | Method of catalytic isomerization processes of 1,3,3,3-tetrafluoropropene for making 2,3,3,3-tetrafluoropropene |
EP07837715A EP2066606B1 (en) | 2006-09-05 | 2007-09-05 | Catalytic isomerization processes of 1,3,3,3-tetrafluoropropene for making 2,3,3,3-tetrafluoropropene |
ES07837715T ES2405363T3 (en) | 2006-09-05 | 2007-09-05 | Catalytic isomerization procedures of 1,3,3,3-tetrafluoropropene to prepare 2,3,3,3-tetrafluoropropene |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US84244906P | 2006-09-05 | 2006-09-05 | |
US60/842,449 | 2006-09-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008030443A1 true WO2008030443A1 (en) | 2008-03-13 |
Family
ID=38988943
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/019318 WO2008030443A1 (en) | 2006-09-05 | 2007-09-05 | Catalytic isomerization processes of 1,3,3,3-tetrafluoropropene for making 2,3,3,3-tetrafluoropropene |
Country Status (5)
Country | Link |
---|---|
US (1) | US7420094B2 (en) |
EP (1) | EP2066606B1 (en) |
CN (1) | CN101535228B (en) |
ES (1) | ES2405363T3 (en) |
WO (1) | WO2008030443A1 (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2008237707B2 (en) * | 2007-04-11 | 2011-06-09 | Mexichem Amanco Holding S.A. De C.V. | Process for isomerising a (hydrohalo) fluoroalkene |
US8536388B2 (en) | 2006-10-03 | 2013-09-17 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing 2,3,3,3-tetrafluoropropene (1234yf) |
US8546623B2 (en) | 2006-10-03 | 2013-10-01 | Mexichem Amanco Holding S.A. De C.V. | Dehydrogenationhalogenation process for the production of C3 -C6-(hydro)fluoroalkenes |
US8552228B2 (en) | 2008-04-09 | 2013-10-08 | Mexichem Amanco Holdings S.A. De C.V. | Process for the preparation of 2,3,3,3-tetrafluoropropene |
WO2014003068A1 (en) * | 2012-06-29 | 2014-01-03 | セントラル硝子株式会社 | Method for producing cis-1,3,3,3-tetrafluoropropene |
US8633340B2 (en) | 2008-04-09 | 2014-01-21 | Mexichem Amanco Holding S.A. De C.V. | Process for the production of chlorinated and fluorinated alkanes and alkenes in the presence of a catalyst |
WO2015059500A1 (en) * | 2013-10-25 | 2015-04-30 | Mexichem Amanco Holding S.A. De C.V. | Process for the isomerisation of c3-7 (hydro)(halo)fluoroalkenes |
US9096489B2 (en) | 2009-04-09 | 2015-08-04 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing 3,3,3-trifluoropropene |
US9115042B2 (en) | 2011-09-14 | 2015-08-25 | Sinochem Lantian Co., Ltd. | Method for preparing 2,3,3,3-tetrafluoropropene |
EP2799415B1 (en) | 2011-12-28 | 2016-06-15 | Asahi Glass Company, Limited | Method and device for purifying 2,3,3,3-tetrafluoropropene and process for producing same |
JP2018027990A (en) * | 2012-06-29 | 2018-02-22 | セントラル硝子株式会社 | Method for producing cis-1,3,3,3-tetrafluoropropene |
US10167242B2 (en) | 2012-05-02 | 2019-01-01 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing a C3-C7 (hydro) fluoroalkene by dehydrohalogenation |
US10513479B2 (en) | 2015-06-02 | 2019-12-24 | Central Glass Company, Limited | Method or producing hydrohalofluoroolefins |
US11406965B2 (en) | 2016-09-07 | 2022-08-09 | Mexichem Fluor S.A. De C.V. | Catalyst and process using the catalyst for manufacturing fluorinated hydrocarbons |
US11452990B2 (en) | 2016-09-07 | 2022-09-27 | Mexichem Fluor S.A. De C.V. | Catalyst and process using the catalyst for manufacturing fluorinated hydrocarbons |
US11866634B2 (en) | 2018-10-26 | 2024-01-09 | The Chemours Company Fc, Llc | HFO-1234ze, HFO-1225zc and HFO-1234yf containing compositions and processes for producing and using the compositions |
US11913681B2 (en) | 2018-10-26 | 2024-02-27 | The Chemours Company Fc, Llc | HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7563936B2 (en) * | 2006-10-27 | 2009-07-21 | Honeywell International Inc | Processes for geometric isomerization of halogenated olefins |
US9255046B2 (en) * | 2003-07-25 | 2016-02-09 | Honeywell International Inc. | Manufacturing process for HFO-1234ze |
US7902410B2 (en) * | 2005-11-03 | 2011-03-08 | Honeywell International Inc. | Process for the manufacture of fluorinated alkanes |
ES2523694T3 (en) * | 2006-07-13 | 2014-11-28 | E.I. Du Pont De Nemours And Company | Catalytic production processes to prepare 1,2,3,3,3-pentafluoropropene |
US8071826B2 (en) | 2008-04-04 | 2011-12-06 | Honeywell International Inc. | Process for the preparation of 2,3,3,3-tetrafluoropropene (HFO-1234yf) |
SG193153A1 (en) | 2008-05-07 | 2013-09-30 | Du Pont | Compositions comprising 1,1,1,2,3-pentafluoropropane or 2,3,3,3- tetrafluoropropene |
LT2634232T (en) * | 2008-05-07 | 2022-06-10 | The Chemours Company Fc, Llc | Compositions |
ES2507575T3 (en) * | 2008-08-22 | 2014-10-15 | Daikin Industries, Ltd. | Procedure for preparing 2,3,3,3-tetrafluoropropene |
EP2349958A2 (en) * | 2008-10-29 | 2011-08-03 | Daikin Industries, Ltd. | Process for preparing 2,3,3,3-tetrafluoropropene |
US8987535B2 (en) | 2008-11-19 | 2015-03-24 | Arkema Inc. | Process for the manufacture of hydrochlorofluoroolefins |
CN105646135A (en) * | 2008-11-19 | 2016-06-08 | 阿科玛股份有限公司 | Process for the manufacture of hydrochlorofluoroolefins |
CA2743842C (en) | 2008-11-19 | 2016-02-09 | Arkema Inc. | Process for the manufacture of hydrofluoroolefins |
US8987534B2 (en) | 2008-11-19 | 2015-03-24 | Arkema Inc. | Process for the manufacture of hydrochlorofluoroolefins |
US8288598B2 (en) * | 2009-01-16 | 2012-10-16 | Honeywell International Inc. | Isomerization of 1,1,3,3-tetrafluoropropene |
JP5418603B2 (en) * | 2009-04-23 | 2014-02-19 | ダイキン工業株式会社 | Method for producing 2,3,3,3-tetrafluoropropene |
MX359434B (en) * | 2009-12-22 | 2018-09-27 | Du Pont | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane. |
US8513474B2 (en) | 2010-06-24 | 2013-08-20 | Honeywell International Inc. | Process for the manufacture of fluorinated olefins |
US8518293B2 (en) * | 2010-09-03 | 2013-08-27 | Honeywell International Inc. | 1,3,3,3-tetrafluoropropene process azeotropes with HF |
US9724684B2 (en) * | 2011-02-21 | 2017-08-08 | The Chemours Company Fc, Llc | Selective catalytical dehydrochlorination of hydrochlorofluorocarbons |
US8822739B2 (en) * | 2012-03-22 | 2014-09-02 | E I Du Pont De Nemours And Company | Catalytic isomerization of 2,3,3,3-tetrafluoropropene |
JP5990990B2 (en) * | 2012-04-16 | 2016-09-14 | セントラル硝子株式会社 | Method for producing cis-1,3,3,3-tetrafluoropropene |
CN103483139B (en) * | 2012-06-15 | 2016-01-27 | 中化蓝天集团有限公司 | A kind of method preparing perfluoro-2-methyl-2-amylene |
US10005705B2 (en) | 2015-11-12 | 2018-06-26 | Honeywell International Inc. | Process for the production of fluorinated cyclobutane |
US9856193B2 (en) | 2015-11-12 | 2018-01-02 | Honeywell International Inc. | Process for the production of fluorinated cyclobutane |
US9790151B2 (en) | 2015-11-12 | 2017-10-17 | Honeywell International Inc. | Process for making 2,3,3,3-tetrafluoropropene and/or vinylidine fluoride |
JP6968162B2 (en) | 2016-11-08 | 2021-11-17 | ハネウェル・インターナショナル・インコーポレーテッドHoneywell International Inc. | Process for producing fluorinated cyclobutane |
JP2021527055A (en) | 2018-06-06 | 2021-10-11 | ハネウェル・インターナショナル・インコーポレーテッドHoneywell International Inc. | Method for producing HFO-1234yf by dehydrochlorinating HCFC-244bb |
US10954177B2 (en) | 2018-08-24 | 2021-03-23 | Honeywell International Inc. | Processes for producing trifluoroiodomethane and trifluoroacetyl iodide |
CN118240528A (en) * | 2018-10-26 | 2024-06-25 | 科慕埃弗西有限公司 | HFO-1234ZE and HFO-1234YF compositions and methods of making and using the same |
CA3123450A1 (en) | 2018-12-21 | 2020-06-25 | Honeywell International, Inc. | Heat transfer methods, systems and fluids |
CN111499489B (en) * | 2019-01-30 | 2023-04-11 | 浙江省化工研究院有限公司 | Isomerization method of fluorine-containing olefin |
US11554956B2 (en) | 2019-04-16 | 2023-01-17 | Honeywell International Inc. | Integrated process and catalysts for manufacturing hydrogen iodide from hydrogen and iodine |
CN115770594A (en) * | 2021-09-06 | 2023-03-10 | 浙江省化工研究院有限公司 | Preparation method and application of hydrophobic catalyst |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2996555A (en) * | 1959-06-25 | 1961-08-15 | Dow Chemical Co | Preparation of 2, 3, 3, 3-tetrafluoropropene |
WO2005108334A1 (en) * | 2004-04-29 | 2005-11-17 | Honeywell International, Inc. | Processes for synthesis of 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2996665A (en) | 1959-03-13 | 1961-08-15 | Itt | Pulse time interval selection and control system |
US5036036A (en) * | 1989-06-13 | 1991-07-30 | E. I. Du Pont De Nemours And Company | Chromium oxide catalyst composition |
US7897823B2 (en) * | 2004-10-29 | 2011-03-01 | E. I. Du Pont De Nemours And Company | Process for production of azeotrope compositions comprising hydrofluoroolefin and hydrogen fluoride and uses of said azeotrope compositions in separation processes |
US7476771B2 (en) * | 2005-11-01 | 2009-01-13 | E.I. Du Pont De Nemours + Company | Azeotrope compositions comprising 2,3,3,3-tetrafluoropropene and hydrogen fluoride and uses thereof |
US7423188B2 (en) * | 2005-11-01 | 2008-09-09 | E. I. Du Pont De Nemours And Company | Azeotrope compositions comprising E-1,3,3,3-tetrafluoropropene and hydrogen fluoride and uses thereof |
WO2008002500A1 (en) | 2006-06-27 | 2008-01-03 | E. I. Du Pont De Nemours And Company | Tetrafluoropropene production processes |
-
2007
- 2007-08-31 US US11/897,582 patent/US7420094B2/en not_active Expired - Fee Related
- 2007-09-05 WO PCT/US2007/019318 patent/WO2008030443A1/en active Application Filing
- 2007-09-05 CN CN200780041195.2A patent/CN101535228B/en not_active Expired - Fee Related
- 2007-09-05 EP EP07837715A patent/EP2066606B1/en not_active Expired - Fee Related
- 2007-09-05 ES ES07837715T patent/ES2405363T3/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2996555A (en) * | 1959-06-25 | 1961-08-15 | Dow Chemical Co | Preparation of 2, 3, 3, 3-tetrafluoropropene |
WO2005108334A1 (en) * | 2004-04-29 | 2005-11-17 | Honeywell International, Inc. | Processes for synthesis of 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene |
Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8536388B2 (en) | 2006-10-03 | 2013-09-17 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing 2,3,3,3-tetrafluoropropene (1234yf) |
US8546623B2 (en) | 2006-10-03 | 2013-10-01 | Mexichem Amanco Holding S.A. De C.V. | Dehydrogenationhalogenation process for the production of C3 -C6-(hydro)fluoroalkenes |
US9790149B2 (en) | 2006-10-03 | 2017-10-17 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing C3-6(hydro)fluoroalkenes by dehydrohalogenating C3-6 halo(hydro) fluoroalkanes in the presence of a zinc chromia catalyst |
US9567275B2 (en) | 2006-10-03 | 2017-02-14 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing C3-6(hydro)fluoroalkenes by dehydrohalogenating C3-6 halo(hydro)fluoroalkanes in the presence of a zinc/chromia catalyst |
US9162946B2 (en) | 2006-10-03 | 2015-10-20 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing C3-6 (hydro)fluoroalkenes by dehydrohalogenating C3-6 halo(hydro)fluoroalkanes in the presence of a zinc/chromia catalyst |
US8742181B2 (en) | 2007-04-11 | 2014-06-03 | Mexichem Amanco Holding S.A. De C.V. | Process for isomerizing A (hydro)fluoroalkene |
AU2008237707C1 (en) * | 2007-04-11 | 2011-10-20 | Mexichem Amanco Holding S.A. De C.V. | Process for isomerising a (hydrohalo) fluoroalkene |
KR101151410B1 (en) | 2007-04-11 | 2012-06-08 | 멕시켐 아만코 홀딩 에스.에이. 데 씨.브이. | Process for isomerising a (hydrohalo)fluoroalkene |
US8410324B2 (en) | 2007-04-11 | 2013-04-02 | Mexichem Amanco Holding, S.A. De C.V. | Process for isomerizing a (hydro)fluoropropene |
AU2008237707B2 (en) * | 2007-04-11 | 2011-06-09 | Mexichem Amanco Holding S.A. De C.V. | Process for isomerising a (hydrohalo) fluoroalkene |
US8629307B2 (en) | 2008-04-09 | 2014-01-14 | Mexichem Amanco S.A. de C.V. | Process for preparing a compound of formula CF3CHFCH2X, wherin X is Cl or F, from 1243zf |
US8552228B2 (en) | 2008-04-09 | 2013-10-08 | Mexichem Amanco Holdings S.A. De C.V. | Process for the preparation of 2,3,3,3-tetrafluoropropene |
US8633340B2 (en) | 2008-04-09 | 2014-01-21 | Mexichem Amanco Holding S.A. De C.V. | Process for the production of chlorinated and fluorinated alkanes and alkenes in the presence of a catalyst |
US8697923B2 (en) | 2008-04-09 | 2014-04-15 | Mexichem Amanco Holding S.A. De C.V. | Process for the preparation of 2,3,3,3,-tetrafluoropropene (R-1234yf) |
US9096489B2 (en) | 2009-04-09 | 2015-08-04 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing 3,3,3-trifluoropropene |
US9115042B2 (en) | 2011-09-14 | 2015-08-25 | Sinochem Lantian Co., Ltd. | Method for preparing 2,3,3,3-tetrafluoropropene |
EP2799415B2 (en) † | 2011-12-28 | 2019-06-12 | AGC Inc. | Method for purifying 2,3,3,3-tetrafluoropropene and process for producing same |
EP2799415B1 (en) | 2011-12-28 | 2016-06-15 | Asahi Glass Company, Limited | Method and device for purifying 2,3,3,3-tetrafluoropropene and process for producing same |
US10167242B2 (en) | 2012-05-02 | 2019-01-01 | Mexichem Amanco Holding S.A. De C.V. | Process for preparing a C3-C7 (hydro) fluoroalkene by dehydrohalogenation |
JP2018027990A (en) * | 2012-06-29 | 2018-02-22 | セントラル硝子株式会社 | Method for producing cis-1,3,3,3-tetrafluoropropene |
WO2014003068A1 (en) * | 2012-06-29 | 2014-01-03 | セントラル硝子株式会社 | Method for producing cis-1,3,3,3-tetrafluoropropene |
US9365472B2 (en) | 2012-06-29 | 2016-06-14 | Central Glass Company, Ltd. | Method for producing cis-1,3,3,3-tetrafluoropropene |
JP2014028799A (en) * | 2012-06-29 | 2014-02-13 | Central Glass Co Ltd | Method for producing cis-1,3,3,3-tetrafluoropropene |
WO2015059500A1 (en) * | 2013-10-25 | 2015-04-30 | Mexichem Amanco Holding S.A. De C.V. | Process for the isomerisation of c3-7 (hydro)(halo)fluoroalkenes |
US10179754B2 (en) | 2013-10-25 | 2019-01-15 | Mexichem Amanco Holding S.A. De C.V. | Process for the isomerisation of C3-7 (hydro)(halo)fluoroalkenes |
EP3296282B1 (en) | 2015-06-02 | 2020-07-29 | Central Glass Company, Limited | Method for producing hydrohalofluoroolefins |
US10513479B2 (en) | 2015-06-02 | 2019-12-24 | Central Glass Company, Limited | Method or producing hydrohalofluoroolefins |
US11406965B2 (en) | 2016-09-07 | 2022-08-09 | Mexichem Fluor S.A. De C.V. | Catalyst and process using the catalyst for manufacturing fluorinated hydrocarbons |
US11452990B2 (en) | 2016-09-07 | 2022-09-27 | Mexichem Fluor S.A. De C.V. | Catalyst and process using the catalyst for manufacturing fluorinated hydrocarbons |
US11866634B2 (en) | 2018-10-26 | 2024-01-09 | The Chemours Company Fc, Llc | HFO-1234ze, HFO-1225zc and HFO-1234yf containing compositions and processes for producing and using the compositions |
US11913681B2 (en) | 2018-10-26 | 2024-02-27 | The Chemours Company Fc, Llc | HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions |
US11927373B2 (en) | 2018-10-26 | 2024-03-12 | The Chemours Company Fc, Llc | HFO-1234ze, HFO-1225zc and HFO-1234yf compositions and processes for producing and using the compositions |
US12018204B2 (en) | 2018-10-26 | 2024-06-25 | The Chemours Company Fc, Llc | HFO-1234ZE, HFO-1225ZC and HFO-1234YF containing compositions and processes for producing and using the compositions |
Also Published As
Publication number | Publication date |
---|---|
US7420094B2 (en) | 2008-09-02 |
ES2405363T3 (en) | 2013-05-30 |
EP2066606B1 (en) | 2013-03-13 |
US20080058562A1 (en) | 2008-03-06 |
EP2066606A1 (en) | 2009-06-10 |
CN101535228B (en) | 2013-07-17 |
CN101535228A (en) | 2009-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7420094B2 (en) | Catalytic isomerization processes of 1,3,3,3-tetrafluoropropene for making 2,3,3,3-tetrafluoropropene | |
US7982073B2 (en) | Catalytic production processes for making tetrafluoropropenes and pentafluoropropenes | |
EP2091897B2 (en) | Processes for the production of fluoropropanes and halopropenes | |
US7872161B2 (en) | Process for producing 2,3,3,3-tetrafluoropropene | |
US8227649B2 (en) | Catalysts and process to manufacture 2,3,3,3-tetrafluoropropene | |
US7906693B2 (en) | Processes for producing 2,3,3,3-tetrafluoropropene, a process for producing 1-chloro-2,3,3,3-pentafluoropropane and azeotropic compositions of 1-chloro-2,3,3,3-tetrafluoropropene with HF | |
US8133406B2 (en) | Processes for producing 2,3,3,3-tetrafluoropropene and/or 1,2,3,3-tetrafluoropropene | |
EP2099733B1 (en) | Process for the synthesis and separation of hydrofluoroolefins | |
US8163964B2 (en) | Processes for producing pentafluoropropenes and certain azeotropes comprising HF and certain halopropenes of the formula C3 HClF4 | |
EP2678300A1 (en) | Catalytic dehydrochlorination of hydrochlorofluorocarbons | |
US20080207963A1 (en) | Preparation of composition containing chromium, oxygen, and either silver or palladium, and their use as catalysts and catalyst precursors | |
US8487145B2 (en) | Catalysts and process to manufacture 2,3,3,3-tetrafluoropropene | |
JP7487173B2 (en) | Compositions and processes for producing chlorofluoroalkenes - Patents.com | |
Rao et al. | Processes for producing pentafluoropropenes and certain azeotropes comprising HF and certain halopropenes of the formula C 3 HClF 4 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780041195.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07837715 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007837715 Country of ref document: EP |