EP1603854A1 - Procede de fabrication de 1,1,1-trifluoroethane - Google Patents
Procede de fabrication de 1,1,1-trifluoroethaneInfo
- Publication number
- EP1603854A1 EP1603854A1 EP04717641A EP04717641A EP1603854A1 EP 1603854 A1 EP1603854 A1 EP 1603854A1 EP 04717641 A EP04717641 A EP 04717641A EP 04717641 A EP04717641 A EP 04717641A EP 1603854 A1 EP1603854 A1 EP 1603854A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- equal
- process according
- molar ratio
- hcfc
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 2
- 239000001257 hydrogen Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 18
- 239000012808 vapor phase Substances 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 150000001844 chromium Chemical class 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- -1 fluoride hydrogen Chemical class 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/42—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the present invention relates to a process for the production of 1,1,1 - trifluoroethane (HFC-143a).
- HFC-143a is used as a component of refrigerant mixtures replacing chlorofluorocarbons.
- Patent application EP-A-714 874 describes the manufacture of HFC-143a from 1,1-Difluoro-1-chloroethane (HCFC-142b) in the vapor phase with an HF / HCFC-142b molar ratio greater than 1.
- the European patent EP-B-714874 teaches that this ratio must be at least 1.3 to avoid the formation of by-products by decomposition of HCFC-142b.
- the invention therefore relates to a process for the production of 1,1,1-trifluoroethane (HFC-143a), according to which 1,1-Difluoro-1-chloroethane (HCFC-142b) is subjected to a vapor phase reaction with hydrogen fluoride (HF) in the presence of a hydrofluorination catalyst, process in which the molar ratio between HCFC-142b and HF introduced into the reaction in the vapor phase is greater than or equal to 1 and less than 1 3.
- HFC-143a 1,1,1-trifluoroethane
- HCFC-142b 1,1-Difluoro-1-chloroethane
- HF hydrogen fluoride
- the HF / HCFC-142b molar ratio is often greater than or equal to 1.02. Preferably, this molar ratio. is greater than or equal to 1.05.
- the HF / HCFCr • 142b molar ratio is often less than or equal to 1.25. Preferably, this molar ratio is less than or equal to 1.20.
- the temperature is generally greater than or equal to 100 ° C. Preferably, the temperature is greater than or equal to 150 ° C. In the process according to the invention, the temperature is generally less than or equal to 400 ° C. Preferably, the temperature is less than or equal to 250 ° C.
- the pressure is generally greater than or equal to 1 bar. Preferably, the pressure is greater than or equal to 5 bar. In the process according to the invention, the pressure is generally less than or equal to 30 bar. Preferably, the pressure is less than or equal to 15 bar.
- the contact time defined as the ratio between the volume of the catalyst divided by the flow rate of HF and HCFC-142b introduced into the reactor is generally greater than or equal to ls. Preferably, the contact time is greater than or equal to 10 s. In the process according to the invention, the contact time defined as the ratio between the volume of the catalyst divided by the flow rate of HF and HCFC-142b introduced into the reactor is generally less than or equal to 200 s. Preferably, the contact time is less than or equal to 50 s.
- the hydrofluorination catalyst can be chosen, for example, from supported or unsupported metal salts. Where appropriate, the support can be, for example, activated carbon.
- the hydrofluorination catalyst can advantageously comprise chromium oxide.
- the amorphous chromium oxide present, before any pre-fluorination treatment generally has a BET / N 2 specific surface of less than or equal to 600 m / g, preferably less than or equal to 400 m 2 / g.
- a particularly preferred catalyst for use in the process according to the invention contains chromium and magnesium. This catalyst can be obtained by a method according to which
- step (d) the dried pulp is subjected to a treatment with hydrogen fluoride at temperatures of 20 to 500 ° C; and the quantities of water-soluble chromium salt (LTI), magnesium hydroxide or magnesium oxide and optionally graphite are chosen in such a way that the dried paste obtained in step (c) contains 3, 5 to 26% by weight, preferably 4.5 to 23% by weight of chromium expressed in the form of Cr2O3, at least 25% by weight of magnesium expressed in the form of MgO and optionally graphite preferably in an amount of 5 to 40% by weight.
- LTI water-soluble chromium salt
- MgO magnesium hydroxide
- optionally graphite optionally graphite
- the molar ratio between HCFC-142b and HF introduced into the vapor phase reaction is greater than or equal to 1.3.
- such a ratio may be implemented greater than or equal to 2.
- the molar ratio between the HCFC-142b and the HF introduced into the reaction in the vapor phase is generally less than or equal to 10.
- this ratio is less than or equal to 5.
- the HCFC-142b used as starting material in the process according to the invention is commercially available. Alternatively, it can be obtained by hydrofluorination from vinylidene chloride or 1,1,1-trichloroethane or their mixtures.
- the stream of reactants introduced into the vapor phase reaction preferably consists essentially of HCFC-142b and hydrogen fluoride.
- Other compounds such as in particular 1,1-dichloro-1-fluoroethane may optionally be present in the stream of reactants introduced into the reaction in the vapor phase.
- the content of such compounds is less than 5 mol% relative to the sum of moles of compounds present in the reactant stream. A content of less than 1 mol% is more particularly preferred.
- the method according to the invention can be carried out in continuous or discontinuous mode.
- a continuous process is preferred.
- the process according to the invention can be implemented in any reactor suitable for carrying out a hydrofluorination process in the vapor phase.
- a tabular reactor made of materials resistant to presence of HF at reaction temperature and pressure, containing a fixed catalyst ht.
- the catalyst was dried for 1 hour at 150 ° C under a nitrogen sweep at a flow rate of 10N 2 / h.
- the catalyst was then fluorinated by an HF / N 2 mixture
- HCFC-142b and HF continuously.
- the HF / HCFC-142b ratio introduced was 1.1.
- the reaction pressure was 10 bar.
- a gas phase was recovered containing HFC-143a which was introduced into a washing column to remove the excess HF and the C1H produced by washing with an aqueous solution of OH.
- the gas leaving this wash analyzed by vapor phase chromatography.
- the conversion of HCFC-142b was 93.5% and the selectivity to HFC-143a was 99.5%.
- the reaction was continued for 600 h without loss of activity or selectivity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0303027 | 2003-03-07 | ||
| FR0303027A FR2852007B1 (fr) | 2003-03-07 | 2003-03-07 | Procede de fabrication de 1,1,1-trifluoroethane |
| PCT/EP2004/002499 WO2004078684A1 (fr) | 2003-03-07 | 2004-03-05 | Procede de fabrication de 1,1,1-trifluoroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1603854A1 true EP1603854A1 (fr) | 2005-12-14 |
Family
ID=32865371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04717641A Withdrawn EP1603854A1 (fr) | 2003-03-07 | 2004-03-05 | Procede de fabrication de 1,1,1-trifluoroethane |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20060189835A1 (https=) |
| EP (1) | EP1603854A1 (https=) |
| JP (1) | JP2006520762A (https=) |
| KR (1) | KR20050120634A (https=) |
| CN (1) | CN100471828C (https=) |
| FR (1) | FR2852007B1 (https=) |
| WO (1) | WO2004078684A1 (https=) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3323374A1 (de) * | 1983-06-29 | 1985-01-10 | Hoechst Ag, 6230 Frankfurt | Katalysatoren fuer fluorierungs- und/oder dismutierungsreaktionen von halogenkohlenwasserstoffen und verfahren zu ihrer herstellung |
| DE3923256A1 (de) * | 1989-07-14 | 1991-01-24 | Hoechst Ag | Verfahren zur herstellung von 1,1,1-trifluor-2-chlorethan |
| DE3930507A1 (de) * | 1989-09-13 | 1991-03-21 | Hoechst Ag | Verfahren zur herstellung von 1,1,1,2-tetrafluorethan |
| WO1996005156A1 (en) * | 1994-08-17 | 1996-02-22 | Alliedsignal Inc. | A process for preparing 1,1,1-trifluoroethane |
| EP0712826A1 (en) * | 1994-11-17 | 1996-05-22 | Elf Atochem North America, Inc. | 1,1,1-Trifluoroethane synthesis using a supported lewis acid |
| US5639924A (en) * | 1994-11-29 | 1997-06-17 | Elf Atochem North America, Inc. | Process for the production of 1,1,1-trifluoroethane |
| ATE178305T1 (de) * | 1994-11-29 | 1999-04-15 | Atochem North America Elf | Adiabatische hydrofluorierung von chlorfluorkohlenwasserstoffen |
| DE19510024C2 (de) * | 1995-03-20 | 1997-02-06 | Hoechst Ag | Verfahren zur Herstellung von Pentafluorethan (R 125) |
| FR2751324B1 (fr) * | 1996-07-16 | 1998-12-04 | Atochem Elf Sa | Synthese du 1,1,1-trifluoroethane par fluoration du 1-chloro-1,1,-difluoroethane |
| FR2807751B1 (fr) * | 2000-04-12 | 2005-05-20 | Solvay | Procede pour la preparation d'un hydro (chloro) fluoroalcane et catalyseur |
-
2003
- 2003-03-07 FR FR0303027A patent/FR2852007B1/fr not_active Expired - Fee Related
-
2004
- 2004-03-05 KR KR1020057016592A patent/KR20050120634A/ko not_active Ceased
- 2004-03-05 CN CNB200480006213XA patent/CN100471828C/zh not_active Expired - Fee Related
- 2004-03-05 JP JP2006504638A patent/JP2006520762A/ja active Pending
- 2004-03-05 WO PCT/EP2004/002499 patent/WO2004078684A1/fr not_active Ceased
- 2004-03-05 EP EP04717641A patent/EP1603854A1/fr not_active Withdrawn
- 2004-03-05 US US10/548,338 patent/US20060189835A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2004078684A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050120634A (ko) | 2005-12-22 |
| CN100471828C (zh) | 2009-03-25 |
| FR2852007B1 (fr) | 2007-05-11 |
| WO2004078684A1 (fr) | 2004-09-16 |
| US20060189835A1 (en) | 2006-08-24 |
| FR2852007A1 (fr) | 2004-09-10 |
| JP2006520762A (ja) | 2006-09-14 |
| CN1759085A (zh) | 2006-04-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20051007 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
| DAX | Request for extension of the european patent (deleted) | ||
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: MROSS, STEFAN Inventor name: MATHIEU, VERONIQUE |
|
| 17Q | First examination report despatched |
Effective date: 20090626 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 20101001 |