EP1603854A1 - Method for producing 1,1,1-trifluoroethane - Google Patents

Method for producing 1,1,1-trifluoroethane

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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
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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.)
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Application number
EP04717641A
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German (de)
French (fr)
Inventor
Veronique Mathieu
Stefan Mross
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Solvay SA
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Solvay SA
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Publication of EP1603854A1 publication Critical patent/EP1603854A1/en
Withdrawn legal-status Critical Current

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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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The inventive method for producing 1,1,1-trifluoroethane (HFC-143a), consists in exposing 1,1-Difluoro-l-chloroethane (HCFC-142b) to a vapour phase reaction with hydrogen fluorine (HF) in the presence of a hydrofluorination catalyst at a molar ratio between HCFC-142b and HF, which is introduced into said vapour phase reaction, equal to or higher than 1 and less than 1.3.

Description

Procédé de fabrication de l.U-trifluoroéthane Process for the manufacture of U-trifluoroethane
La présente invention concerne un procédé de fabrication de 1,1,1 - trifluoroéthane (HFC-143a).The present invention relates to a process for the production of 1,1,1 - trifluoroethane (HFC-143a).
Le HFC-143a est utilisé comme constituant de mélanges réfrigérants remplaçant les chlorofluorocarbures.HFC-143a is used as a component of refrigerant mixtures replacing chlorofluorocarbons.
La demande de brevet EP-A-714874 décrit la fabrication de HFC-143a au départ de 1,1-Difluoro-l-chloroéthane (HCFC- 142b) en phase vapeur avec un rapport molaire HF/HCFC-142b supérieur à 1. Le brevet européen EP-B-714874 enseigne que ce rapport doit être d'au moins 1,3 pour éviter la formation de sous produits par décomposition du HCFC-142b.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.
Il était souhaitable de mettre à disposition un procédé sélectif de fabrication de HFC-143a au départ de HCFC-142b, permettant d'atteindre une bonne productivité volumique et minimisant la nécessité d'opérations d'épuration à l'issue de la réaction d'hydrofluoration. L'invention concerne dès lors un procédé pour la fabrication de 1,1,1- trifluoroéthane (HFC-143a), selon lequel on soumet du 1,1-Difluoro-l- chloroéthane (HCFC- 142b) à une réaction en phase vapeur avec du fluorure d'hydrogène (HF) en présence d'un catalyseur d'hydrofluoration, procédé dans lequel le rapport molaire entre le HCFC- 142b et le HF introduits dans la réaction en phase vapeur est supérieur ou égal à 1 et inférieur à 1,3.It was desirable to provide a selective process for the production of HFC-143a from HCFC-142b, making it possible to achieve good volume productivity and minimizing the need for purification operations at the end of the reaction. hydrofluorination. 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.
H a été trouvé, de manière surprenante et contrairement à l'enseignement du document EP 714874, qu'il est possible d'obtenir du HFC-143a au départ de HCFC- 142b de manière efficace et sélective tout en travaillant avec un rapport HF/HCFC-142b proche de 1. Dans le procédé selon l'invention on observe en plus une bonne stabilité de l'activité du catalyseur dans le temps.It has been found, surprisingly and contrary to the teaching of document EP 714874, that it is possible to obtain HFC-143a from HCFC-142b in an efficient and selective manner while working with an HF / HCFC-142b close to 1. In the process according to the invention, good stability of the activity of the catalyst is observed over time.
Dans le procédé selon l'invention, le rapport molaire HF/HCFC-142b est souvent supérieur ou égal à 1,02. De préférence, ce rapport molaire. est supérieur ou égal à 1,05. Dans le procédé selon l'invention, le rapport molaire HF/HCFCr • 142b est souvent inférieur ou égal à 1,25. De préférence, ce rapport molaire est inférieur ou égal à 1,20.In the process according to the invention, 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. In the process according to the invention, 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.
Dans le procédé selon l'invention, la température est généralement supérieure ou égale à 100°C. De préférence, la température est supérieure ou égale à 150°C. Dans le procédé selon l'invention, la température est généralement inférieure ou égale à 400°C. De préférence, la température est inférieure ou égale à 250°C.In the process according to the invention, 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.
Dans le procédé selon l'invention, la pression est généralement supérieure ou égale à 1 bar. De préférence, la pression est supérieure ou égale à 5 bar. Dans le procédé selon l'invention, la pression est généralement inférieure ou égale à 30 bar. De préférence, la pression est inférieure ou égale à 15 bar. Dans le procédé selon l'invention, le temps de contact défini comme le rapport entre le volume du catalyseur divisé par le débit de HF et HCFC-142b introduit dans le réacteur est généralement supérieur ou égal à ls. De préférence, le temps de contact est supérieur ou égal à 10s. Dans le procédé selon l'invention, le temps de contact défini comme le rapport entre le volume du catalyseur divisé par le débit de HF et HCFC- 142b introduit dans le réacteur est généralement inférieur ou égal à 200 s. De préférence, le temps de contact est inférieur ou égal à 50 s. Dans le procédé selon l'invention, le catalyseur d'hydrofluoration peut être choisi par exemple parmi les sels de métaux supportés ou non. Le cas échéant le support peut être, par exemple, du charbon actif.In the process according to the invention, 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. 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 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. In the process according to the invention, the hydrofluorination catalyst can be chosen, for example, from supported or unsupported metal salts. Where appropriate, the support can be, for example, activated carbon.
Le catalyseur d'hydrofluoration peut de manière avantageuse comprendre de l'oxyde de chrome. Un oxyde de chrome amorphe présentant avant un éventuel traitement de préfluoration une surface spécifique BET/N2 supérieure ou égale à 100 m2/g donne de bons résultats. Un oxyde de chrome amorphe présentant une telle surface spécifique supérieure ou égale à 200 m2/g est préféré.The hydrofluorination catalyst can advantageously comprise chromium oxide. An amorphous chromium oxide having, before any pre-fluorination treatment, a BET / N 2 specific surface greater than or equal to 100 m 2 / g gives good results. An amorphous chromium oxide having such a specific surface greater than or equal to 200 m 2 / g is preferred.
Le cas échéant l'oxyde de chrome amorphe présente avant un éventuel traitement de préfluoration généralement une surface spécifique BET/N2 inférieure ou égale à 600 m /g, de préférence inférieure ou égale à 400 m2/g.Where appropriate, 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.
Un catalyseur particulièrement préféré pour la mise en œuvre dans le procédé selon l'invention, contient du chrome et du magnésium. Ce catalyseur peut être obtenu par une méthode selon laquelleA 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
(a) on fait réagir un sel hydrosoluble de chrome (ILT) avec de l'hydroxyde de magnésium ou de l'oxyde de magnésium ainsi que facultativement du graphite en présence d'eau ;(a) reacting a water-soluble chromium salt (ILT) with magnesium hydroxide or magnesium oxide and optionally graphite in the presence of water;
(b) on transforme le mélange réactionnel obtenu en pâte ;(b) the reaction mixture obtained is transformed into a paste;
(c) on sèche la pâte ;(c) the dough is dried;
(d) on soumet la pâte séchée à un traitement avec du fluorure d'hydrogène à des températures de 20 à 500°C ; et on choisit les quantités de sel hydrosoluble de chrome (LTI), d'hydroxyde de magnésium ou d'oxyde de magnésium ainsi que facultativement de graphite respectivement de telle manière que la pâte séchée obtenue à l'étape (c) contienne de 3,5 à 26% en poids, de préférence de 4,5 à 23% en poids de chrome exprimé sous la forme de Cr2O3, au moins 25% en poids de magnésium exprimé sous forme de MgO et éventuellement du graphite de préférence en une quantité de 5 à 40% en poids. La fabrication d'un tel catalyseur est décrite par exemple dans la demande EP-A-733611 dont le contenu à ce sujet est incorporé par référence dans la présente demande. Dans un autre aspect, il a été trouvé qu'avec le catalyseur contenant du , chrome et du magnésium décrit ci avant, toutes autres caractéristiques restant telles que décrit plus haut, des avantages particuliers de stabilité de l'activité du catalyseur sont également obtenus lorsque le rapport molaire entre le HCFC- 142b et le HF introduits dans la réaction en phase vapeur est supérieur ou égal à 1,3. Dans cet aspect particulier, on peut mettre en œuvre un tel rapport supérieur ou égal à 2. Dans cet aspect particulier, le rapport molaire entre le HCFC-142b et le HF introduits dans la réaction en phase vapeur est généralement inférieur ou égal à 10. De préférence, dans cet aspect particulier, ce rapport est inférieur ou égal à 5. Le HCFC- 142b utilisé comme produit de départ dans le procédé selon l'invention est commercialement disponible. Alternativement il peut être obtenu par hydrofluoration au départ de chlorure de vinylidène ou de 1,1,1 - trichloroéthane ou leurs mélanges.(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. The manufacture of such a catalyst is described for example in application EP-A-733611, the content of which on this subject is incorporated by reference in the present application. In another aspect, it has been found that with the catalyst containing chromium and magnesium described above, all other characteristics remaining as described above, particular advantages of stability of the activity of the catalyst are also obtained when the molar ratio between HCFC-142b and HF introduced into the vapor phase reaction is greater than or equal to 1.3. In this particular aspect, such a ratio may be implemented greater than or equal to 2. In this particular aspect, 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. Preferably, in this particular aspect, 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.
Le courant de réactifs introduits dans la réaction en phase vapeur est, de préférence, constitué essentiellement de HCFC-142b et de fluorure d'hydrogène. D'autres composés tels que notamment du 1,1-dichloro-l-fluoroéthane peuvent éventuellement être présents dans le courant de réactifs introduits dans la réaction en phase vapeur. De préférence la teneur en tels composés est inférieure à 5% molaire par rapport à la somme de moles de composés présents dans le courant de réactifs. Une teneur inférieure à 1% molaire est plus particulièrement préférée.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. Preferably, 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.
Le procédé selon l'invention peut être réalisé en, mode continu ou discontinu. Un procédé continu est préféré.The method according to the invention can be carried out in continuous or discontinuous mode. A continuous process is preferred.
Le procédé selon l'invention peut être mis en œuvre dans tout réacteur approprié à la réalisation d'un procédé d'hydrofluoration en phase vapeur. Citons en particulier tin réacteur tabulaire réalisé en matériaux résistant à la présence de HF à la température et pression de la réaction, contenant un ht fixe de catalyseur.The process according to the invention can be implemented in any reactor suitable for carrying out a hydrofluorination process in the vapor phase. Let us cite in particular a tabular reactor made of materials resistant to presence of HF at reaction temperature and pressure, containing a fixed catalyst ht.
L'exemple ci-après entend illustrer l'invention sans toutefois la hmiter.The example below is intended to illustrate the invention without, however, limiting it.
Exemple Dans un réacteur tubulaire en Hastelloy B2 d'un volume de 70 ml, on a introduit un catalyseur contenant 4,6 % en poids de Cr exprimé sous forme deExample A catalyst containing 4.6% by weight of Cr expressed in the form of a Hastelloy B2 tubular reactor with a volume of 70 ml was introduced.
Cr2O3, du Mg et du graphite, obtenu conformément à l'exemple du document EPCr 2 O 3 , Mg and graphite, obtained in accordance with the example of document EP
733611.733,611.
On a séché le catalyseur pendant 1 heure à 150°C sous un balayage d'azote à un débit de 10N2/h. Le catalyseur a ensuite été fluoré par un mélange HF/N2 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
(11 1 HF/h - 201 N2/h) pendant 1 heure à 200°C, puis 1 heure à 250°C, 6 heures à(11 1 HF / h - 201 N 2 / h) for 1 hour at 200 ° C, then 1 hour at 250 ° C, 6 hours at
300°C et 8 heures à 350°C.300 ° C and 8 hours at 350 ° C.
Après fluoration, on a chauffé à une température de 200°C. On a introduit duAfter fluorination, it was heated to a temperature of 200 ° C. We introduced
HCFC-142b et du HF en continu. Le rapport HF/HCFC-142b introduit était de 1,1. La pression de la réaction était de 10 bar. A l'issue de la réaction on a récupéré une phase gazeuse contenant du HFC-143a que l'on a introduit dans une colonne de lavage pour éliminer le HF excédentaire et le C1H produit par lavage avec une solution aqueuse de OH. Le gaz sortant de ce lavage a analysé par chromatographie en phase vapeur. La conversion de HCFC-142b était de 93,5% et la sélectivité en HFC-143a était de 99,5%. Les 0,5% d'impuretés contenaient 50% de HCFC-141b. La réaction a été poursuivie pendant 600h sans perte d'activité ou de sélectivité. HCFC-142b and HF continuously. The HF / HCFC-142b ratio introduced was 1.1. The reaction pressure was 10 bar. At the end of the reaction, 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 0.5% impurities contained 50% HCFC-141b. The reaction was continued for 600 h without loss of activity or selectivity.

Claims

R E VE ND I C A T I O N SR E VE ND I C A T I O N S
1 - Procédé pour la fabrication de 1,1,1-trifluoroéthane (HFC-143a), selon lequel on soumet du 1,1-Difluoro-l-chloroéthane (HCFC-142b) à une réaction en phase vapeur avec du fluorure d'hydrogène (HF) en présence d'un catalyseur d'hydrofluoration, procédé dans lequel le rapport molaire entre le HCFC-142b et le HF introduits dans la réaction en phase vapeur est supérieur ou égal à 1 et inférieur à 1,3.1 - 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 fluoride hydrogen (HF) in the presence of a hydrofluorination catalyst, process in which the molar ratio between the HCFC-142b and the HF introduced into the reaction in vapor phase is greater than or equal to 1 and less than 1.3.
2 - Procédé selon la revendication 1, dans lequel le rapport molaire est supérieur ou égal à 1,02.2 - Process according to claim 1, in which the molar ratio is greater than or equal to 1.02.
3 - Procédé selon la revendication 2, dans lequel le rapport molaire est supérieur ou égal à 1,05.3 - Process according to claim 2, wherein the molar ratio is greater than or equal to 1.05.
4 - Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le rapport molaire est inférieur ou égal à 1,25.4 - Process according to any one of claims 1 to 3, wherein the molar ratio is less than or equal to 1.25.
5 - Procédé selon la revendication 4, dans lequel le rapport molaire est inférieur ou égal à 1,20.5 - Process according to claim 4, wherein the molar ratio is less than or equal to 1.20.
6 - Procédé selon l'une quelconque des revendications 1 à 5, dans lequel la température de la réaction est de 100 à 400°C.6 - Process according to any one of claims 1 to 5, wherein the reaction temperature is 100 to 400 ° C.
7 - Procédé selon l'une quelconque des revendications 1 à 6 dans lequel la pression de la réaction est de 1 à 30 bar.7 - Process according to any one of claims 1 to 6 wherein the reaction pressure is from 1 to 30 bar.
8 - Procédé selon l'une quelconque des revendications 1 à 7 dans lequel le temps de contact est de 1 à 200 s.8 - Method according to any one of claims 1 to 7 wherein the contact time is from 1 to 200 s.
9 - Procédé selon l'une quelconque des revendications 1 à 8 dans lequel le catalyseur d'hydrofluoration comprend de l'oxyde de chrome.9 - Process according to any one of claims 1 to 8 wherein the hydrofluorination catalyst comprises chromium oxide.
10 - Procédé selon la revendication 9 dans lequel le catalyseur contient du chrome et du magnésium et le catalyseur peut être obtenu par une méthode selon laquelle (a) on fait réagir un sel hydrosoluble de chrome (IE) avec de l'hydroxyde de magnésium ou de l'oxyde de magnésium ainsi que facultativement du graphite en présence d'eau ;10 - Process according to claim 9 wherein the catalyst contains chromium and magnesium and the catalyst can be obtained by a method according to which (a) reacting a water-soluble chromium (IE) salt with magnesium hydroxide or magnesium oxide and optionally graphite in the presence of water;
(b) on transforme le mélange réactionnel, obtenu en pâte ; (c) on sèche la pâte ;(b) the reaction mixture obtained is transformed into a paste; (c) the dough is dried;
(d) on soumet la pâte séchée à un traitement avec du fluorure d'hydrogène à des températures de 20 à 500 °C ; et on choisit les quantités de sel hydrosoluble de chrome (ÏÏI), d'hydroxyde de magnésium ou d'oxyde de magnésium respectivement de telle manière que la pâte séchée obtenue à l'étape (c) contienne de 3,5 à 26% en poids, de chrome exprimé sous forme de Cr2O3 et au moins 25% en poids de magnésium exprimé sous forme de MgO. (d) the dried pulp is subjected to a treatment with hydrogen fluoride at temperatures of 20 to 500 ° C; and the amounts of water-soluble chromium salt (III), magnesium hydroxide or magnesium oxide are chosen respectively so that the dried paste obtained in step (c) contains from 3.5 to 26% by weight, of chromium expressed in the form of Cr2O3 and at least 25% by weight of magnesium expressed in the form of MgO.
EP04717641A 2003-03-07 2004-03-05 Method for producing 1,1,1-trifluoroethane Withdrawn EP1603854A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0303027A FR2852007B1 (en) 2003-03-07 2003-03-07 PROCESS FOR PRODUCING 1,1,1-TRIFLUOROETHANE
FR0303027 2003-03-07
PCT/EP2004/002499 WO2004078684A1 (en) 2003-03-07 2004-03-05 Method for producing 1,1,1-trifluoroethane

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EP (1) EP1603854A1 (en)
JP (1) JP2006520762A (en)
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CN (1) CN100471828C (en)
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WO (1) WO2004078684A1 (en)

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DE3323374A1 (en) * 1983-06-29 1985-01-10 Hoechst Ag, 6230 Frankfurt CATALYSTS FOR FLUORATION AND / OR DISMUTATION REACTIONS OF HALOGEN HYDROCARBONS AND METHOD FOR THE PRODUCTION THEREOF
DE3923256A1 (en) * 1989-07-14 1991-01-24 Hoechst Ag PROCESS FOR THE PREPARATION OF 1,1,1-TRIFLUOR-2-CHLORETHANE
DE3930507A1 (en) * 1989-09-13 1991-03-21 Hoechst Ag METHOD FOR PRODUCING 1,1,1,2-TETRAFLUORETHANE
EP0777637A1 (en) * 1994-08-17 1997-06-11 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
ES2129718T3 (en) * 1994-11-29 1999-06-16 Atochem North America Elf ADIABATIC HYDROFLUORATION OF HYDROCHLOROFLUOROCARBONS.
US5639924A (en) * 1994-11-29 1997-06-17 Elf Atochem North America, Inc. Process for the production of 1,1,1-trifluoroethane
DE19510024C2 (en) * 1995-03-20 1997-02-06 Hoechst Ag Process for the preparation of pentafluoroethane (R 125)
FR2751324B1 (en) * 1996-07-16 1998-12-04 Atochem Elf Sa SYNTHESIS OF 1,1,1-TRIFLUOROETHANE BY FLUORINATION OF 1-CHLORO-1,1, -DIFLUOROETHANE
FR2807751B1 (en) * 2000-04-12 2005-05-20 Solvay PROCESS FOR THE PREPARATION OF A HYDRO (CHLORO) FLUOROALCANE AND CATALYST

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WO2004078684A1 (en) 2004-09-16
KR20050120634A (en) 2005-12-22
FR2852007A1 (en) 2004-09-10
JP2006520762A (en) 2006-09-14
CN100471828C (en) 2009-03-25
US20060189835A1 (en) 2006-08-24
FR2852007B1 (en) 2007-05-11

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