EP2125677A1 - Method for producing 1,1-difluoroethane - Google Patents

Method for producing 1,1-difluoroethane

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Publication number
EP2125677A1
EP2125677A1 EP08761905A EP08761905A EP2125677A1 EP 2125677 A1 EP2125677 A1 EP 2125677A1 EP 08761905 A EP08761905 A EP 08761905A EP 08761905 A EP08761905 A EP 08761905A EP 2125677 A1 EP2125677 A1 EP 2125677A1
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EP
European Patent Office
Prior art keywords
process according
difluoroethane
chromium
nickel
fluorination
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
EP08761905A
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German (de)
French (fr)
Inventor
Anne Pigamo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Arkema France SA
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Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2125677A1 publication Critical patent/EP2125677A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/122—Halides of copper

Definitions

  • the subject of the present invention is a process for the manufacture of 1,1-difluoroethane by fluorination in the gaseous phase by means of hydrofluoric acid (HF) of 1,2-dichloroethane (or D12, of formula CH 2 CICH 2 Cl), in the presence of a catalyst.
  • HF hydrofluoric acid
  • D12 1,2-dichloroethane
  • the 1,1-difluoroethane of formula CHsCHF 2 is a hydrofluoroalkane or hydrofluorocarbon (HFA or HFC) also known under the name F152a. It is a substitute for chlorofluorocarbons (CFCs) that may be useful in industrial refrigeration, but also as a foaming agent or as an aerosol propellant. It can be used alone or mixed.
  • HFA or HFC hydrofluoroalkane or hydrofluorocarbon
  • F152a hydrofluorocarbon
  • CFCs chlorofluorocarbons
  • Example 8 of US 6274780 describes the reaction of 1,2-dichloroethane with hydrofluoric acid at 225 ° C in the presence of a catalyst containing aluminum, chromium and fluorine in a 1: 1 atomic ratio. 6.
  • US 4147733 discloses the fluorination reaction between a chlorinated aliphatic hydrocarbon and an aqueous solution of hydrofluoric acid at a temperature between 275 and 425 ° C in the presence of a metal fluoride catalyst, preferably a fluoride of aluminum, nickel, chromium or their mixture.
  • a metal fluoride catalyst preferably a fluoride of aluminum, nickel, chromium or their mixture.
  • the process for producing 1,1-difluoroethane by catalytic gas phase fluorination of 1,2-dichloroethane with anhydrous hydrofluoric acid is characterized in that the reaction is carried out in the presence of a mixed catalyst composed of oxides , halides, oxyhalides and / or inorganic salts of nickel and chromium, optionally deposited on a support.
  • Nickel and chromium are preferably present in a nickel / chromium atomic ratio of between 0.5 and 5, and advantageously close to 1.
  • mixed catalysts composed of oxides, halides and / or oxyhalides of nickel and chromium deposited on a support consisting of aluminum fluoride or a mixture of aluminum fluoride and alumina as described, for example, in patents FR 2669022 and EP-B-0609124.
  • the fluorination reaction of D12 with anhydrous HF can be carried out at a temperature of between 200 and 400 ° C., preferably between 250 and 350 ° C.
  • the contact time for the reaction according to the invention may be between 1 and 120 sec, preferably between 10 and 90 sec.
  • the molar ratio HF / D12 may be between 1 and 40, preferably between 10 and 20.
  • fluorination reaction according to the invention can be carried out at atmospheric pressure, it is preferred to operate under pressure, and advantageously between 10 and 16 bar absolute.
  • This content may vary between 0.02 and 1 mol% relative to the mixture of gaseous reactants entering the reactor.
  • the process according to the present invention can be carried out in a reactor constructed from corrosion-resistant materials, for example HASTELLOY, INCONEL and MONEL.
  • the method according to the present invention further has the advantage of reducing the amount of vinyl chloride and thus the separation of the products from the reaction is facilitated.
  • alumina Grace HSA previously pretreated in a fixed bed at 280 0 C under an HF / air mixture containing between 5 and 10% HF.
  • the starting alumina is in the form of beads having a diameter of between 0.5 and 2 mm. Its specific surface is about 220 m 2 / g and its pore volume of 1.3 cm 3 / g.
  • two aqueous solutions are prepared:
  • the other contains 62 g of water, 55 g of chromic acid CrO ⁇ and 130 g of nickel chloride NiC 4 (dissolution of the mixture at 50 ° C. for 2.5 hours).
  • the two solutions are introduced simultaneously and progressively onto the alumina support maintained at 40 ° C. and stirred. After a maturation step under nitrogen, the catalyst is dried under nitrogen, then under vacuum at 65 ° C. and then at 90 ° C. for 6 hours.
  • This pilot comprises a reactor consisting of an inconel tube with an internal diameter of 38 mm and a length of 500 mm, placed vertically in a tubular electric furnace.
  • a thermowell with an outside diameter of 6 mm is placed coaxially in the furnace and allows a temperature reading along the catalytic bed using four thermocouples stages.
  • a coil wound around the reactor and traversed vertically from bottom to top allows the reactants to be preheated before entering the reactor.
  • a layer of corundum of 30 ml above the catalytic bed ensures a homogeneous distribution of the gaseous reactants.
  • a control valve maintains the desired pressure. The gaseous flow at the inlet and the outlet of the reactor is analyzed by gas phase chromatography.
  • 300 ml (256 g) of the solid described above are introduced into the reactor and then dried overnight in the presence of nitrogen (2 mol / h) at 300 ° C. and atmospheric pressure.
  • the dried solid is then activated (still at atmospheric pressure) under a stream comprising anhydrous hydrofluoric acid for 15 minutes before being placed under pure HF at 300 ° C.
  • the pressure is then regulated very gradually until it reaches 15 ° C. Absolute bars.
  • the reagents air and 1,2-dichloroethane
  • the feed rates are such that the molar ratio HF / D12 is equal to the value indicated in the table for each example, the molar ratio O2 / DI2 is equal to 0.03, the contact time is 60 seconds.
  • the temperature is maintained at 300 ° C.
  • the result is recorded in the table.
  • the majority product obtained at the reaction outlet is 1,1-difluoroethane.
  • GPC analysis also reveals vinyl chloride, vinyl fluoride, 1-chloro-2-fluoroethane, 1,1-chlorofluoroethane, 1,1-dichloroethane and carbon dioxide. The results are expressed using the conversion and selectivity defined below.
  • Mol D12 input is the amount of moles of D12 at the reactor inlet and mol D12 output is the amount of D12 at the reactor outlet.
  • mol xi is the amount of moles of D12 at the reactor inlet
  • the time given for each data refers to the age of the catalyst at the time of analysis relative to the start of the reaction.

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  • 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)

Abstract

The invention relates to a method for producing 1,1-difluoroethane. The invention more precisely relates to a method for producing 1,1-difluoroethane by the gaseous-phase fluorination of 1,2-dichloroethane (or D12 of the formula CH<SUB>2</SUB>CICH<SUB>2</SUB>CI) with anhydrous hydrofluoric acid (HF) in the presence of a mixed catalyst.

Description

PROCEDE DE FABRICATION DU 1,1-DIFLUOROETHANE PROCESS FOR PRODUCING 1,1-DIFLUOROETHANE
La présente invention a pour objet un procédé de fabrication du 1 ,1- difluoroéthane par fluoration en phase gazeuse au moyen de l'acide fluorhydrique (HF) du 1 ,2-dichloroéthane (ou D12, de formule CH2CICH2CI), en présence d'un catalyseur.The subject of the present invention is a process for the manufacture of 1,1-difluoroethane by fluorination in the gaseous phase by means of hydrofluoric acid (HF) of 1,2-dichloroethane (or D12, of formula CH 2 CICH 2 Cl), in the presence of a catalyst.
Le 1 ,1-difluoroéthane de formule CHsCHF2 est un hydrofluoroalcane ou hydrofluorocarbure (HFA ou HFC) connu également sous la dénomination F152a. C'est un substitut des chlorofluorocarbures (CFC) qui peut être utile dans la réfrigération industrielle, mais également comme agent d'expansion des mousses ou comme propulseur d'aérosol. Il peut être utilisé seul ou en mélange.The 1,1-difluoroethane of formula CHsCHF 2 is a hydrofluoroalkane or hydrofluorocarbon (HFA or HFC) also known under the name F152a. It is a substitute for chlorofluorocarbons (CFCs) that may be useful in industrial refrigeration, but also as a foaming agent or as an aerosol propellant. It can be used alone or mixed.
Il est connu de faire réagir un mélange de 1 ,2-dichloroéthane et/ou chlorure de vinyle avec de l'acide fluorhydrique, à une température comprise entre 200 et 5000C, en présence d'un catalyseur à base d'oxyde de chrome (CA 832502). L'exemple 2 de ce document décrit la réaction entre le 1 ,2- dichloroéthane et l'acide fluorhydrique en phase gazeuse en présence d'un catalyseur à base d'oxyde de chrome (Cr2Os) supporté sur de l'alumine-γ à 3500C. Dans ces conditions le fluorure de vinyle et le 1 ,1 -difluoroéthane représentent seulement 20 % des produits de la réaction, le reste (i.e. 80 %) étant le chlorure de vinyle. En outre, le chlorure de vinyle présente l'inconvénient de former un azéotrope avec le 1 ,1-difluoroéthane (US 5874657) et est donc très difficile à séparer par distillation conventionnelle.It is known to react a mixture of 1,2-dichloroethane and / or vinyl chloride with hydrofluoric acid, at a temperature of between 200 and 500 ° C., in the presence of a catalyst based on aluminum oxide. chromium (CA 832502). Example 2 of this document describes the reaction between 1,2-dichloroethane and hydrofluoric acid in the gas phase in the presence of a catalyst based on chromium oxide (Cr 2 Os) supported on alumina. γ 0 to 350 C. Under these conditions vinyl fluoride and 1, 1-difluoroethane only represent 20% of the reaction products, the rest (ie 80%) being the vinyl chloride. In addition, vinyl chloride has the disadvantage of forming an azeotrope with 1,1-difluoroethane (US 5874657) and is therefore very difficult to separate by conventional distillation.
L'exemple 8 du document US 6274780 décrit la réaction du 1 ,2- dichloroéthane avec de l'acide fluorhydrique à 225°C en présence d'un catalyseur contenant l'aluminium, le chrome et le fluor dans un rapport atomique 1 :1 :6.Example 8 of US 6274780 describes the reaction of 1,2-dichloroethane with hydrofluoric acid at 225 ° C in the presence of a catalyst containing aluminum, chromium and fluorine in a 1: 1 atomic ratio. 6.
Le document US 4147733 décrit la réaction de fluoration entre un hydrocarbure aliphatique chloré et une solution aqueuse de l'acide fluorhydrique à une température comprise entre 275 et 425°C en présence d'un catalyseur à base de fluorure métallique, de préférence un fluorure d'aluminium, de nickel, de chrome ou leur mélange. L'inconvénient des procédés tels que décrits dans l'art antérieur cité est la conversion insuffisante du 1 ,2-dichloroéthane et/ou la sélectivité peu élevée en 1 ,1-difluoroéthane.US 4147733 discloses the fluorination reaction between a chlorinated aliphatic hydrocarbon and an aqueous solution of hydrofluoric acid at a temperature between 275 and 425 ° C in the presence of a metal fluoride catalyst, preferably a fluoride of aluminum, nickel, chromium or their mixture. The disadvantage of the processes as described in the cited prior art is the insufficient conversion of 1,2-dichloroethane and / or the low selectivity to 1,1-difluoroethane.
Il a maintenant été trouvé un procédé de fabrication du 1 ,1- difluoroéthane ne présentant pas les inconvénients de l'art antérieur.It has now been found a method of manufacturing 1,1-difluoroethane does not have the disadvantages of the prior art.
Le procédé de fabrication du 1 ,1-difluoroéthane par fluoration catalytique en phase gazeuse, du 1 ,2-dichloroéthane avec de l'acide fluorhydrique anhydre est caractérisé en ce que l'on opère en présence d' un catalyseur mixte composé d'oxydes, halogénures, oxyhalogénures et/ou sels minéraux de nickel et de chrome, éventuellement déposé sur support.The process for producing 1,1-difluoroethane by catalytic gas phase fluorination of 1,2-dichloroethane with anhydrous hydrofluoric acid is characterized in that the reaction is carried out in the presence of a mixed catalyst composed of oxides , halides, oxyhalides and / or inorganic salts of nickel and chromium, optionally deposited on a support.
Comme support, on peut citer notamment l'alumine, le fluorure d'aluminium ou l'oxyfluorure d'aluminium.As support, mention may be made in particular of alumina, aluminum fluoride or aluminum oxyfluoride.
Le nickel et le chrome sont de préférence présents dans un rapport atomique nickel/chrome compris entre 0,5 et 5, et avantageusement voisin de 1.Nickel and chromium are preferably present in a nickel / chromium atomic ratio of between 0.5 and 5, and advantageously close to 1.
Pour cette invention, on préférera des catalyseurs mixtes composés d'oxydes, d'halogénures et/ou oxyhalogénures de nickel et de chrome déposés sur un support constitué de fluorure d'aluminium ou d'un mélange de fluorure d'aluminium et d'alumine tels que décrits par exemple dans les brevets FR 2669022 et EP-B-0609124.For this invention, preference will be given to mixed catalysts composed of oxides, halides and / or oxyhalides of nickel and chromium deposited on a support consisting of aluminum fluoride or a mixture of aluminum fluoride and alumina as described, for example, in patents FR 2669022 and EP-B-0609124.
Conformément au procédé selon l'invention, la réaction de fluoration du D12 par de l'HF anhydre peut être conduite à une température comprise entre 200 et 4000C, de préférence entre 250 et 3500C.According to the process according to the invention, the fluorination reaction of D12 with anhydrous HF can be carried out at a temperature of between 200 and 400 ° C., preferably between 250 and 350 ° C.
Le temps de contact pour la réaction selon l'invention peut être compris entre 1 et 120 sec, de préférence entre 10 et 90 sec.The contact time for the reaction according to the invention may be between 1 and 120 sec, preferably between 10 and 90 sec.
Le rapport molaire HF/D12 peut être compris entre 1 et 40, de préférence entre 10 et 20.The molar ratio HF / D12 may be between 1 and 40, preferably between 10 and 20.
Bien que la réaction de fluoration selon l'invention puisse être mise en œuvre à la pression atmosphérique, on préfère opérer sous pression, et avantageusement entre 10 et 16 bars absolus.Although the fluorination reaction according to the invention can be carried out at atmospheric pressure, it is preferred to operate under pressure, and advantageously between 10 and 16 bar absolute.
Bien qu'il ne soit pas nécessaire, il peut être judicieux d'introduire avec les réactifs de l'oxygène ou du chlore à faible teneur. Cette teneur peut varier entre 0,02 et 1 % molaire par rapport au mélange des réactifs gazeux entrant dans le réacteur.Although it is not necessary, it may be advisable to introduce low oxygen or low chlorine with the reagents. This content may vary between 0.02 and 1 mol% relative to the mixture of gaseous reactants entering the reactor.
Le procédé selon la présente invention peut être mis en œuvre dans un réacteur construit à partir de matériaux résistants à la corrosion par exemple HASTELLOY, INCONEL et MONEL.The process according to the present invention can be carried out in a reactor constructed from corrosion-resistant materials, for example HASTELLOY, INCONEL and MONEL.
Le procédé selon la présente invention présente en outre l'avantage de réduire la quantité de chlorure de vinyle et ainsi la séparation des produits issus de la réaction est facilitée.The method according to the present invention further has the advantage of reducing the amount of vinyl chloride and thus the separation of the products from the reaction is facilitated.
PARTIE EXPERIMENTALEEXPERIMENTAL PART
Préparation du catalyseurCatalyst preparation
Dans un évaporateur rotatif, on place 343g d'un support d'alumine Grâce HSA préalablement prétraité en lit fixe à 2800C sous un mélange HF/air contenant entre 5 et 10% d'HF. L'alumine de départ se présente sous la forme de billes de diamètre compris entre 0,5 et 2mm. Sa surface spécifique est environ de 220 m2/g et son volume poreux de 1 ,3 cm3/g. Par ailleurs, on prépare deux solutions aqueuses :In a rotary evaporator, 343 g of a support of alumina Grace HSA previously pretreated in a fixed bed at 280 0 C under an HF / air mixture containing between 5 and 10% HF. The starting alumina is in the form of beads having a diameter of between 0.5 and 2 mm. Its specific surface is about 220 m 2 / g and its pore volume of 1.3 cm 3 / g. In addition, two aqueous solutions are prepared:
- l'une contient 81g de méthanol et 8 g d'eau- one contains 81g of methanol and 8g of water
- l'autre contient 62g d'eau, 55g d'acide chromique CrOβ et 130g de chlorure de nickel NiC^ (dissolution du mélange à 500C pendant 2h30).the other contains 62 g of water, 55 g of chromic acid CrOβ and 130 g of nickel chloride NiC 4 (dissolution of the mixture at 50 ° C. for 2.5 hours).
Les deux solutions sont introduites simultanément et progressivement sur le support d'alumine maintenu à 400C et agité. Après une étape de maturation sous azote, le catalyseur est séché sous azote, puis sous vide à 65°C, puis vers 90°C pendant 6 heures.The two solutions are introduced simultaneously and progressively onto the alumina support maintained at 40 ° C. and stirred. After a maturation step under nitrogen, the catalyst is dried under nitrogen, then under vacuum at 65 ° C. and then at 90 ° C. for 6 hours.
On charge 500g de solide imprégné dans un réacteur tubulaire en inconel. Le catalyseur est tout d'abord séché sous balayage d'azote à 320°C, à pression atmosphérique. Il est ensuite fluoré en présence d'un mélange HF/N2 (5 à 10 % d'HF dans l'azote) à 3200C puis jusqu'à 390°C. L'alimentation HF est ensuite coupée. Le catalyseur est refroidi sous azote. Réaction de fluoration500 g of impregnated solid are loaded into a tubular reactor in inconel. The catalyst is first dried under a nitrogen sweep at 320 ° C. at atmospheric pressure. It is then fluorinated in the presence of an HF / N2 mixture (5 to 10% of HF in nitrogen) at 320 ° C. and then up to 390 ° C. The HF supply is then cut off. The catalyst is cooled under nitrogen. Fluoridation reaction
Les exemples ci-dessous ont été réalisés à l'aide d'un pilote de fluoration en phase gaz en continu. Ce pilote comprend un réacteur constitué d'un tube en inconel d'un diamètre interne de 38 mm et d'une longueur de 500 mm, placé verticalement dans un four électrique tubulaire. Un puits thermométrique de diamètre extérieur de 6 mm est placé coaxialement dans le four et permet une lecture de température le long du lit catalytique à l'aide de quatre thermocouples étages.The examples below were carried out using a continuous gas phase fluorination pilot. This pilot comprises a reactor consisting of an inconel tube with an internal diameter of 38 mm and a length of 500 mm, placed vertically in a tubular electric furnace. A thermowell with an outside diameter of 6 mm is placed coaxially in the furnace and allows a temperature reading along the catalytic bed using four thermocouples stages.
Un serpentin enroulé autour du réacteur et traversé verticalement de bas en haut permet de préchauffer les réactifs avant l'entrée dans le réacteur. Une couche de corindon de 30 ml au dessus du lit catalytique permet d'assurer une distribution homogène des réactifs gazeux. Une vanne de régulation permet de maintenir la pression souhaitée. Le flux gazeux à l'entrée et la sortie du réacteur est analysé par chromatographie phase gaz.A coil wound around the reactor and traversed vertically from bottom to top allows the reactants to be preheated before entering the reactor. A layer of corundum of 30 ml above the catalytic bed ensures a homogeneous distribution of the gaseous reactants. A control valve maintains the desired pressure. The gaseous flow at the inlet and the outlet of the reactor is analyzed by gas phase chromatography.
Mode opératoire généralGeneral procedure
300ml (256g) du solide décrit ci-dessus sont introduits dans le réacteur, puis séché pendant une nuit en présence d'azote (2 mol/h) à 300° C et pression atmosphérique. Le solide séché est ensuite activé (toujours à pression atmosphérique) sous un flux comprenant de l'acide fluorhydrique anhydre pendant 15 minutes avant d'être placé sous HF pur à 3000C. La pression est ensuite régulée très progressivement jusqu'à atteindre 15 bars absolus. Les réactifs (l'air et le 1 ,2-dichloroéthane) sont ensuite introduits. Les débits alimentés sont tels que le rapport molaire HF/D12 est égal à valeur indiquée dans le tableau pour chaque exemple, le rapport molaire O2/DI2 est égal à 0,03, le temps de contact est de 60 secondes. La température est maintenue à 3000C. Le résultat est consigné dans le tableau. Le produit majoritaire obtenu en sortie de réaction est le 1 ,1-difluoroéthane. L'analyse CPG révèle également du chlorure de vinyle, du fluorure de vinyle, du 1-chloro-2-fluoroéthane, du 1 ,1- chlorofluoroéthane, du 1 ,1-dichloroéthane et du dioxyde de carbone. Les résultats sont exprimés à l'aide de la conversion et de la sélectivité définis ci-après.300 ml (256 g) of the solid described above are introduced into the reactor and then dried overnight in the presence of nitrogen (2 mol / h) at 300 ° C. and atmospheric pressure. The dried solid is then activated (still at atmospheric pressure) under a stream comprising anhydrous hydrofluoric acid for 15 minutes before being placed under pure HF at 300 ° C. The pressure is then regulated very gradually until it reaches 15 ° C. Absolute bars. The reagents (air and 1,2-dichloroethane) are then introduced. The feed rates are such that the molar ratio HF / D12 is equal to the value indicated in the table for each example, the molar ratio O2 / DI2 is equal to 0.03, the contact time is 60 seconds. The temperature is maintained at 300 ° C. The result is recorded in the table. The majority product obtained at the reaction outlet is 1,1-difluoroethane. GPC analysis also reveals vinyl chloride, vinyl fluoride, 1-chloro-2-fluoroethane, 1,1-chlorofluoroethane, 1,1-dichloroethane and carbon dioxide. The results are expressed using the conversion and selectivity defined below.
/-> - r^ o /n/ \ molD,? entrée - molD,? sortie / -> - r ^ o / n / \ molD ,? input - molD ,? exit
Conversion D12 (%) = - -^ molDn entréeConvert D12 (%) = - - ^ molD n input
Mol D12 entrée est la quantité de moles de D12 à l'entrée du réacteur et mol D12 sortie est la quantité de D12 à la sortie du réacteur. mol xiMol D12 input is the amount of moles of D12 at the reactor inlet and mol D12 output is the amount of D12 at the reactor outlet. mol xi
Sélectivité xi (%) = xi : produit en sortieSelectivity xi (%) = xi: output product
\ molxi\ molxi
Le temps indiqué pour chaque donnée se rapporte à l'âge du catalyseur au moment de l'analyse par rapport au début de la réaction.The time given for each data refers to the age of the catalyst at the time of analysis relative to the start of the reaction.

Claims

REVENDICATIONS
1 ) Procédé de fabrication du 1 ,1-difluoroéthane par fluoration catalytique en phase gazeuse, du 1 ,2-dichloroéthane avec de l'acide fluorhydrique anhydre est caractérisé en ce que l'on opère en présence d'un catalyseur mixte composé d'oxydes, halogénures, oxyhalogénures et/ou sels minéraux de nickel et de chrome, éventuellement déposé sur support.1) Process for producing 1,1-difluoroethane by catalytic gas phase fluorination of 1,2-dichloroethane with anhydrous hydrofluoric acid is characterized in that it is carried out in the presence of a mixed catalyst composed of oxides, halides, oxyhalides and / or inorganic salts of nickel and chromium, optionally deposited on a support.
2) Procédé selon la revendication 1 caractérisé en ce que le support, est l'alumine, le fluorure d'aluminium ou l'oxyfluorure d'aluminium.2) Process according to claim 1 characterized in that the support is alumina, aluminum fluoride or aluminum oxyfluoride.
3) Procédé selon la revendication 1 ou 2 caractérisé en ce que le nickel et le chrome sont présents dans un rapport atomique nickel/chrome compris entre 0,5 et 5, et avantageusement voisin de 1.3) Process according to claim 1 or 2 characterized in that the nickel and chromium are present in a nickel / chromium atomic ratio of between 0.5 and 5, and preferably close to 1.
4) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que la température de fluoration est comprise entre 200 et 4000C, de préférence entre 250 et 3500C.4) Process according to any one of the preceding claims, characterized in that the fluorination temperature is between 200 and 400 0 C, preferably between 250 and 350 0 C.
5) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le temps de contact est compris entre 1 et 120 sec, de préférence entre 10 et 90 sec.5) Method according to any one of the preceding claims characterized in that the contact time is between 1 and 120 sec, preferably between 10 and 90 sec.
6) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le rapport molaire HF/D12 est compris entre 1 et 40, de préférence entre 10 et 20.6) Process according to any one of the preceding claims, characterized in that the molar ratio HF / D12 is between 1 and 40, preferably between 10 and 20.
7) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que la réaction de fluoration est mise en œuvre sous pression, et de préférence entre 10 et 16 bars absolus.7) Process according to any one of the preceding claims characterized in that the fluorination reaction is carried out under pressure, and preferably between 10 and 16 bar absolute.
8) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que de l'oxygène ou du chlore à faible teneur sont introduits avec les réactifs. 8) Process according to any one of the preceding claims characterized in that oxygen or low-content chlorine are introduced with the reagents.
EP08761905A 2007-01-29 2008-01-08 Method for producing 1,1-difluoroethane Withdrawn EP2125677A1 (en)

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FR0752929A FR2911870B1 (en) 2007-01-29 2007-01-29 PROCESS FOR PRODUCING 1,1-DIFLUOROETHANE
PCT/FR2008/050029 WO2008107578A1 (en) 2007-01-29 2008-01-08 Method for producing 1,1-difluoroethane

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CN102698778B (en) * 2012-06-15 2014-03-05 浙江师范大学 Catalyst for preparing vinyl fluoride and 1,1-difluoroethane by using acetylene fluoride and preparation method for catalyst
CN112608216B (en) * 2020-11-23 2022-01-21 浙江衢化氟化学有限公司 Method for co-production of 1, 1-difluoroethane and vinyl chloride

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US4147733A (en) * 1978-05-22 1979-04-03 The Dow Chemical Company Fluorination of chlorinated hydrocarbons
FR2669022B1 (en) * 1990-11-13 1992-12-31 Atochem PROCESS FOR THE MANUFACTURE OF TETRAFLUORO-1,1,1,2-ETHANE.
US6274780B1 (en) * 1995-07-11 2001-08-14 E. I. Du Pont De Nemours And Company Catalysts for halogenated hydrocarbon processing and their preparation and use

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FR2911870B1 (en) 2009-03-20
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