WO2003068717A1 - Composition based on stabilized trichloroethylene used as a starting material - Google Patents

Composition based on stabilized trichloroethylene used as a starting material Download PDF

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WO2003068717A1
WO2003068717A1 PCT/FR2003/000306 FR0300306W WO03068717A1 WO 2003068717 A1 WO2003068717 A1 WO 2003068717A1 FR 0300306 W FR0300306 W FR 0300306W WO 03068717 A1 WO03068717 A1 WO 03068717A1
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tri
ppm
stabilized
trichlorethylene
composition based
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PCT/FR2003/000306
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French (fr)
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Régis Loze
Philippe Leduc
Patrick Mathieu
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Atofina
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Priority to AU2003222350A priority Critical patent/AU2003222350A1/en
Priority to EP03717365A priority patent/EP1476412A1/en
Publication of WO2003068717A1 publication Critical patent/WO2003068717A1/en

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    • 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
    • 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
    • C07C17/093—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
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • 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

Definitions

  • Composition based on stabilized trichlorethylene usable as raw material Composition based on stabilized trichlorethylene usable as raw material.
  • HFA hydrofluoroalkanes
  • This reaction can be carried out either in the liquid phase in the presence of catalysts such as SbC ⁇ at approximately 100 ° C, under a pressure of approximately 15 bars, or in the gas phase at 250 ° C in the presence of a chromium on alumina catalyst.
  • 133a is an intermediate of choice for obtaining the 134a obtained according to the reaction CF3CH 2 CI + HF> CF3CH 2 F + HCI.
  • This reaction can be carried out in the vapor phase at 350 ° C. under a pressure of 15 bars, in the presence of NiCr / Al 2 O 3 .
  • TRI trichlorethylene
  • CHCI 2 CHCI 2 and / or CH 2 CICCI 3 CHCI CCI 2 + HCI cracking
  • aliphatic and cycloaliphatic amines such as triethylamine (US 1,925,602), diisopropylamine, triisopropylamine, cyclohexylamine (FR 2010281) which are HCI sensors; phenols such as p-tert-butylphenol, p-amylphenol, thymol (US 2,155,723) which are used as antioxidants; oxides such as butylene oxide (US 2,981,760) are also used to capture HCI. These compounds can be used alone or better in combination, (at a rate of a few tens of ppm).
  • the Applicant has found that a TRI stabilized against acidity by a few ppm of diisopropylamine (DIPA) acidifies over time, especially in air.
  • DIPA diisopropylamine
  • the conversion of the TRI is equal to 99.4% after 2 hours and 99.3% after 100 hours, which indicates that it there is no deterioration of the catalyst.
  • this procedure requires the use of two columns of zeolite: one in operation and one in regeneration and therefore a high investment in material (and of limited efficiency) for the productivity of an industrial unit .
  • SbCI 5 which consists in using a TRI without stabilizer coming directly from manufacturing, that is to say a TRI which has not been stored. This procedure can only be carried out if there is a TRI preparation unit adjacent to an HFA production unit so as to avoid storage of said TRI.
  • a subject of the invention is therefore the use of a composition based on trichlorethylene (TRI) stabilized as a raw material in particular for the synthesis of HFAs, characterized in that said composition consists of TRI, by at least one aliphatic amine used in weight quantities such that the weight content of total nitrogen is less than or equal to 3 ppm and, preferably between 1 ppm and 2.5 ppm, and with at least one phenol used in weight quantities at least equal to 3 ppm and, preferably between 5 ppm and 10 ppm.
  • TRI trichlorethylene
  • aliphatic amines which can be used according to the present invention, mention will be made of triethylamine, diethylamine, diisopropylamine, triisopropylamine and diisobutylamine.
  • the present invention relates more particularly to the use of diisopropylamine (or DIPA).
  • phenols which can be used according to the present invention mention will be made of paratertiobutylphenol, paratertioamylphenol, thymol (5-methyl-2-isopropyl-1-phenol).
  • the present invention particularly relates to the use of thymol.
  • an amount by weight of aliphatic amine will be used which makes it possible to obtain a weight content of total nitrogen less than or equal to 3 ppm.
  • the composition according to the invention can be prepared by simple mixing of the compounds with freshly prepared trichlorethylene. This mixing can be carried out on an unstabilized TRI storage tank or more particularly in line at the outlet of the distillation column.
  • composition according to the invention can be used very particularly for the preparation of HFAs such as 134a from 133a.
  • the TRI used is obtained by pyrolysis at approximately 500 ° C. of tetrachloroethanes (sym. And dissym.). After separation of the HCl formed, the TRI is separated from the tetrachloroethones, washed and neutralized. It is then dried by distillation.
  • Different compositions of stabilized TRI are prepared by adding the following stabilizers: thymol, diisopropylamine (DIPA), in proportions as indicated in table 1 to a TRI leaving directly from the distillation column. Aging tests are then carried out in air or under nitrogen at 40 ° C. of compositions 2 to 5 and of unstabilized TRI. To do this, hermetically closed 2 I glass vials containing 2 kg of product to be tested in air or under nitrogen are placed in an oven maintained at 40 ° C.
  • DIPA diisopropylamine
  • the pH is measured initially and after 75 days will be known for the non-stabilized TRI, where the pH is measured after 30 days.
  • the pH is measured on the aqueous extract of a sample of the TRI composition mixed with water according to a TRI / water ratio of 1/1.
  • composition 5 The synthesis of 134a is carried out using composition 5, according to the reactions:
  • Step 1 / is carried out in the liquid phase in the presence of SbC 4 as a catalyst at approximately 100 ° C. under a pressure of 15 bars.
  • Step 2 / is carried out in the vapor phase at 350 ° C. at 15 bars in the presence of a Ni / Cr catalyst on alumina.

Abstract

The invention relates to the use of a composition on the basis of stabilized trichloroethylene with an amine and a phenol as starting materials, particularly for synthesizing hydrofluoroalkanes (HFA).

Description

Composition à base de trichloroethylene stabilisé utilisable comme matière première. Composition based on stabilized trichlorethylene usable as raw material.
La présente invention concerne l'utilisation du trichloroethylene CHCI = CCI 2 stabilisé comme matière première.The present invention relates to the use of trichlorethylene CHCI = CCI 2 stabilized as a raw material.
Elle concerne tout particulièrement l'utilisation du trichloroethylene stabilisé pour la préparation des hydrofluoroalcanes (HFA) tels que notamment le 133a (CH2CICF3), le 134a (CF3CH2F) ou le 125 (CF3CHF2). Ainsi, le 133a peut être obtenu selon la réaction : CHCI = CCI2 + 3HF > CF3CH2CI + 2HCIIt relates in particular to the use of stabilized trichlorethylene for the preparation of hydrofluoroalkanes (HFA) such as in particular 133a (CH 2 CICF 3 ), 134a (CF 3 CH 2 F) or 125 (CF 3 CHF 2 ). Thus, 133a can be obtained according to the reaction: CHCI = CCI 2 + 3HF> CF 3 CH 2 CI + 2HCI
Cette réaction peut être réalisée soit en phase liquide en présence de catalyseurs tels que SbC^ à environ 100°C, sous une pression d'environ 15 bars, soit en phase gazeuse à 250°C en présence d'un catalyseur chrome sur alumine. Le 133a est un intermédiaire de choix pour l'obtention du 134a obtenu selon la réaction CF3CH2CI + HF > CF3CH2F + HCI. Cette réaction peut être réalisée en phase vapeur à 350°C sous une pression de 15 bars, en présence de NiCr /Al2O3.This reaction can be carried out either in the liquid phase in the presence of catalysts such as SbC ^ at approximately 100 ° C, under a pressure of approximately 15 bars, or in the gas phase at 250 ° C in the presence of a chromium on alumina catalyst. 133a is an intermediate of choice for obtaining the 134a obtained according to the reaction CF3CH 2 CI + HF> CF3CH 2 F + HCI. This reaction can be carried out in the vapor phase at 350 ° C. under a pressure of 15 bars, in the presence of NiCr / Al 2 O 3 .
Le trichloroethylene, ci-après désigné par TRI peut être obtenu par pyrolyse des tétrachloroéthanes (symétrique et/ou dissymétrique) selon la réaction :The trichlorethylene, hereinafter designated by TRI, can be obtained by pyrolysis of the tetrachloroethanes (symmetrical and / or asymmetrical) according to the reaction:
CHCI2CHCI2 et/ou CH2CICCI3 CHCI= CCI2 + HCI crackingCHCI 2 CHCI 2 and / or CH 2 CICCI 3 CHCI = CCI 2 + HCI cracking
Il est connu que le TRI non stabilisé se décompose lentement en présence d'air et de lumière en HCI, oxydes de carbone, phosgene et chlorure de dichloroacétyle. Cette décomposition est accélérée par la chaleur (> 100°C), et l'humidité (Ullmann's Encyclopedia of Industrial Chemistry Ad, pages 299 et 300 5ème édition, 1986).It is known that unstabilized TRI decomposes slowly in the presence of air and light in HCI, carbon oxides, phosgene and dichloroacetyl chloride. This decomposition is accelerated by heat (> 100 ° C) and humidity (Ullmann's Encyclopedia of Industrial Chemistry Ad pages 299 and 300 5th edition, 1986).
L'eau, les acides provenant de l'extérieur, certa ns métaux et certains sels métalliques, de même que les produits de décomposition du trichloréthylène peuvent également favoriser la décomposition. Dans ce cas, il se forme des produits acides tels que l'acide chlorhydrique, des produits toxiques tels que le phosgene ou des substances goudronneuses pouvant avoir une influence néfaste lors du stockage, du transport et de l'utilisation. C'est pourquoi il est important d'empêcher la décomposition du trichloréthylène et d'éviter l' influence néfaste des produits de décomposition. Aussi, pour palier ces inconvénients, de très nombreux composés ont été préconisés comme agents inhibiteurs de la décomposition, ou stabilisants du TRI.Water, acids from outside, some metals and some metal salts, as well as the decomposition products of trichlorethylene can also promote decomposition. In this case, acid products such as hydrochloric acid are formed, toxic products such as phosgene or tarry substances which can have a harmful influence during storage, transport and use. This is why it is important to prevent the decomposition of trichlorethylene and to avoid the harmful influence of the decomposition products. Also, to overcome these drawbacks, very many compounds have been recommended as inhibitors of decomposition, or stabilizers of TRI.
Parmi les composés, les plus utilisés, on citera les aminés aliphatiques et cycloaliphatiques, tels que la triéthylamine (US 1,925,602), la diisopropylamine, la triisopropylamine, la cyclohexylamine (FR 2010281) qui sont des capteurs d'HCI ; les phénols tels que le p-tert-butylphénol, le p-amylphénol, le thymol (US 2,155,723) qui sont utilisés comme antioxydants ; les oxydes tels que l'oxyde de butylène (US 2,981,760) sont également utilisés pour capter HCI. Ces composés pouvant être utilisés seuls ou mieux en combinaison, (à raison de quelques dizaines de ppm).Among the compounds, the most used, there will be mentioned aliphatic and cycloaliphatic amines, such as triethylamine (US 1,925,602), diisopropylamine, triisopropylamine, cyclohexylamine (FR 2010281) which are HCI sensors; phenols such as p-tert-butylphenol, p-amylphenol, thymol (US 2,155,723) which are used as antioxidants; oxides such as butylene oxide (US 2,981,760) are also used to capture HCI. These compounds can be used alone or better in combination, (at a rate of a few tens of ppm).
Ainsi, par exemple, la demanderesse a constaté qu'un TRI stabilisé contre l'acidité par quelques ppm de diisopropylamine (DIPA) s'acidifie dans le temps notamment sous air. La demanderesse, sans qu'elle soit tenue par une quelconque explication, pense que sous l'effet de l'air et de la lumière le TRI se dégrade (lentement) en libérant des produits acides tels que HCI qui sont susceptibles de consommer de la DIPA.Thus, for example, the Applicant has found that a TRI stabilized against acidity by a few ppm of diisopropylamine (DIPA) acidifies over time, especially in air. The Applicant, without being bound by any explanation, believes that under the effect of air and light the TRI degrades (slowly) by releasing acid products such as HCI which are likely to consume DIPA.
Afin de remédier à cet état de fait, la demanderesse a trouvé qu'en ajoutant au TRI stabilisé DIPA quelques ppm de thymol le pH de ce TRI stabilisé n'évoluait plus sous air. Cependant, lorsque le TRI doit être utilisé comme matière première, ces stabilisants, présents pour protéger ledit TRI, sont susceptible de réagir soit avec les produits formés, soit avec les réactifs mis en oeuvre.In order to remedy this state of affairs, the applicant has found that by adding a few ppm of thymol to the stabilized TRI DIPA, the pH of this stabilized TRI no longer changes in air. However, when TRI must be used as a raw material, these stabilizers, present to protect said TRI, are capable of reacting either with the products formed, or with the reagents used.
Ainsi, lorsque le TRI est utilisé comme matière première pour la synthèse des HFA comme mentionné précédemment, les aminés aliphatiques notamment, sont susceptibles de se complexer avec les catalyseurs utilisés pour la synthèse desdits HFA.Thus, when TRI is used as a raw material for the synthesis of HFAs as mentioned above, the aliphatic amines in particular are likely to complex with the catalysts used for the synthesis of said HFAs.
Ces stabilisants peuvent être éliminés du TRI avant son utilisation par distillation. Mais cette façon de procéder est compliquée et nécessite des installations coûteuses. Dans la demande de brevet japonaise JP-A-6-321819, on décrit une méthode d'élimination d'aminés aliphatiques, notamment de la diisopropylamine (DIPA) utilisée en des quantités allant de 15 ppm à 100 ppm, qui consiste à mettre en contact le TRI stabilisé avec ladite DIPA avec une zéolite ayant des particules allant de 3 Â à 5 Â. Ainsi, par exemple, dans un réacteur en acier inoxydable de 2 litres contenant 1,8 litre de zéolite 4 A, on introduit en continu du TRI contenant 15 ppm de DIPA à raison de 4 litres /heure. Des prélèvements effectués à 100, 200 et 400 heure en sortie de colonne indiquent l'absence de DIPA dans le TRI (analyses effectuées par chromatographie en phase gazeuse).These stabilizers can be removed from the TRI before use by distillation. However, this procedure is complicated and requires expensive installations. In Japanese patent application JP-A-6-321819, a method of removing aliphatic amines, in particular diisopropylamine (DIPA) used in amounts ranging from 15 ppm to 100 ppm, is described, which consists in contact the stabilized TRI with said DIPA with a zeolite having particles ranging from 3 Å to 5 Å. Thus, for example, in a 2-liter stainless steel reactor containing 1.8 liters of 4 A zeolite, TRI is continuously introduced containing 15 ppm of DIPA at a rate of 4 liters / hour. Samples taken at 100, 200 and 400 hours at the column outlet indicate the absence of DIPA in the TRI (analyzes carried out by gas chromatography).
L'utilisation de ce TRI ainsi purifié est utilisé comme matière première pour la synthèse de 134a selon les réactions :The use of this thus purified TRI is used as a raw material for the synthesis of 134a according to the reactions:
1/ CHCI = CCI2 + 3HF > CF3CH2CI + 2HCI1 / CHCI = CCI 2 + 3HF> CF 3 CH 2 CI + 2HCI
2/ CF3CH2CI + HF CF3CH2F + HCI2 / CF 3 CH 2 CI + HF CF 3 CH 2 F + HCI
Les 2 étapes sont effectuées en phase vapeur en présence d'un catalyseur chrome sur alumine. L'étape 1/ est effectuée à 250°C sous une pression de 4 kg/cm 2 avec un rapport molaire HF/TRI = 6 et un débit de 1 000 hr-1 et l'étape 2/ est réalisée à 350°C sous une pression de 4 kg/cm2 avec un rapport molaire HF/CF3CH2CI = 4. La conversion du TRI est égale à 99,4 % après 2 heures et 99,3 % après 100 heures, ce qui indique qu' il n'y a pas de détérioration du catalyseur. Bien que donnant de bons résultats, cette façon de procéder nécessite l'utilisation de deux colonnes de zéolite : une en fonctionnement et une en régénération et donc un investissement en matériel élevé (et d'efficacité limitée) pour la productivité d'une unité industrielle.The 2 stages are carried out in vapor phase in the presence of a chromium catalyst on alumina. Step 1 / is carried out at 250 ° C under a pressure of 4 kg / cm 2 with an HF / TRI molar ratio = 6 and a flow rate of 1000 hr-1 and step 2 / is carried out at 350 ° C under a pressure of 4 kg / cm 2 with a HF / CF3CH 2 CI molar ratio = 4. The conversion of the TRI is equal to 99.4% after 2 hours and 99.3% after 100 hours, which indicates that it there is no deterioration of the catalyst. Although giving good results, this procedure requires the use of two columns of zeolite: one in operation and one in regeneration and therefore a high investment in material (and of limited efficiency) for the productivity of an industrial unit .
Dans la demande de brevet DE 2719021 (Bayer), on décrit un procédé de préparation de 133a en phase liquide à partir du TRI selon la réaction :In patent application DE 2719021 (Bayer), a process for the preparation of 133a in the liquid phase from the TRI is described according to the reaction:
CH = CCI2 + 3HF > CF3CH2CI + 2HCICH = CCI 2 + 3HF> CF 3 CH 2 CI + 2HCI
SbCI5 qui consiste à utiliser un TRI sans stabilisant provenant directement de la fabrication, c'est-à-dire un TRI n'ayant pas été stocké. Cette façon de procéder ne peut être effectuée que si l'on possède une unité de préparation de TRI jouxtant une unité de production de HFA de façon à éviter le stockage dudit TRI.SbCI 5 which consists in using a TRI without stabilizer coming directly from manufacturing, that is to say a TRI which has not been stored. This procedure can only be carried out if there is a TRI preparation unit adjacent to an HFA production unit so as to avoid storage of said TRI.
La demanderesse a maintenant trouvé qu'elle pouvait s'affranchir des moyens de purifications précédemment mentionnés et qu' il était possible d'utiliser un TRI stocké, stabilisé avec des quantités adéquates de stabilisantThe Applicant has now found that it could overcome the previously mentioned purification means and that it was possible to use a stored TRI, stabilized with adequate amounts of stabilizer
(tel quel), sans avoir à les éliminer pour la synthèse des HFA sans qu'il y ait une consommation rédhibitoire de catalyseur.(as is), without having to eliminate them for the synthesis of HFAs without there being a prohibitive consumption of catalyst.
L' invention a donc pour objet l'utilisation d'une composition à base de trichloroethylene (TRI) stabilisé comme matière première notamment pour la synthèse des HFA, caractérisée en ce que ladite composition est constituée par du TRI, par au moins une aminé aliphatique utilisée en des quantités pondérales telles que la teneur pondérale en azote totale soit inférieure ou égale à 3 ppm et, de préférence comprise entre 1 ppm et 2,5 ppm, et par au moins un phénol utilisé en des quantités pondérales au moins égales à 3 ppm et, de préférence comprises entre 5 ppm et 10 ppm.A subject of the invention is therefore the use of a composition based on trichlorethylene (TRI) stabilized as a raw material in particular for the synthesis of HFAs, characterized in that said composition consists of TRI, by at least one aliphatic amine used in weight quantities such that the weight content of total nitrogen is less than or equal to 3 ppm and, preferably between 1 ppm and 2.5 ppm, and with at least one phenol used in weight quantities at least equal to 3 ppm and, preferably between 5 ppm and 10 ppm.
A titre d'aminés aliphatiques utilisables selon la présente invention, on citera la triéthylamine, la diéthylamine, la diisopropylamine, la triisopropylamine, la diisobutylamine.As aliphatic amines which can be used according to the present invention, mention will be made of triethylamine, diethylamine, diisopropylamine, triisopropylamine and diisobutylamine.
La présente invention concerne tout particulièrement l'utilisation de la diisopropylamine (ou DIPA).The present invention relates more particularly to the use of diisopropylamine (or DIPA).
A titre de phénols utilisables selon la présente invention, on citera le paratertiobutylphénol, le paratertioamylphénol, le thymol (5-méthyl-2-isopropyl- 1-phénol). La présente invention concerne tout particulièrement l'utilisation du thymol.As phenols which can be used according to the present invention, mention will be made of paratertiobutylphenol, paratertioamylphenol, thymol (5-methyl-2-isopropyl-1-phenol). The present invention particularly relates to the use of thymol.
Selon la présente invention, on utilisera une quantité pondérale d'aminé aliphatique permettant d'obtenir une teneur pondérale en azote totale inférieure ou égale à 3 ppm. La composition selon l'invention peut être préparée par simple mélange des composés avec le trichloroethylene fraîchement préparé. Ce mélange peut être réalisé sur un bac de stockage de TRI non stabilisé ou plus particulièrement en ligne en sortie de la colonne de distillation.According to the present invention, an amount by weight of aliphatic amine will be used which makes it possible to obtain a weight content of total nitrogen less than or equal to 3 ppm. The composition according to the invention can be prepared by simple mixing of the compounds with freshly prepared trichlorethylene. This mixing can be carried out on an unstabilized TRI storage tank or more particularly in line at the outlet of the distillation column.
La composition selon l' invention est utilisable tout particulièrement pour la préparation des HFA tel que le 134a à partir du 133a.The composition according to the invention can be used very particularly for the preparation of HFAs such as 134a from 133a.
Les exemples qui suivent illustrent l' invention.The following examples illustrate the invention.
Exemples :Examples:
Le TRI utilisé est obtenu par pyrolyse à environ 500°C de tétrachloroéthanes (sym. et dissym.). Après séparation de l'HCI formé, le TRI est séparé des tétrachloroéthnes, lavé et neutralisé. Il est ensuite séché par distillation. On prépare différentes compositions de TRI stabilisé en ajoutant les stabilisants suivants : thymol, diisopropylamine (DIPA), en des proportions telles qu' indiquées dans le tableau 1 à un TRI sortant directement de la colonne de distillation. On effectue ensuite des tests de vieillissement sous air ou sous azote à 40°C des compositions 2 à 5 et du TRI non stabilisé. Pour ce faire, on place dans une étuve maintenue à 40°C des flacons de verre de 2 I hermétiquement fermés, contenant 2 kg de produit à tester sous air ou sous azote.The TRI used is obtained by pyrolysis at approximately 500 ° C. of tetrachloroethanes (sym. And dissym.). After separation of the HCl formed, the TRI is separated from the tetrachloroethones, washed and neutralized. It is then dried by distillation. Different compositions of stabilized TRI are prepared by adding the following stabilizers: thymol, diisopropylamine (DIPA), in proportions as indicated in table 1 to a TRI leaving directly from the distillation column. Aging tests are then carried out in air or under nitrogen at 40 ° C. of compositions 2 to 5 and of unstabilized TRI. To do this, hermetically closed 2 I glass vials containing 2 kg of product to be tested in air or under nitrogen are placed in an oven maintained at 40 ° C.
Le pH est mesuré initialement et au bout de 75 jours saur pour le TRI non stabilisé, où le pH est mesuré au bout de 30 jours.The pH is measured initially and after 75 days will be known for the non-stabilized TRI, where the pH is measured after 30 days.
Le pH est mesuré sur l'extrait aqueux d'une prise d'échantillon de la composition de TRI mélangé avec de l'eau selon un rapport TRI / eau de 1/1.The pH is measured on the aqueous extract of a sample of the TRI composition mixed with water according to a TRI / water ratio of 1/1.
Les résultats sont reportés dans le tableau ci-après.
Figure imgf000006_0001
The results are reported in the table below.
Figure imgf000006_0001
TABLEAU 1TABLE 1
Essai de synthèse du 134a :134a synthesis test:
On effectue la synthèse du 134a en utilisant la composition 5, selon les réactions :The synthesis of 134a is carried out using composition 5, according to the reactions:
1/ CHCI = CCI2 + 3HF > CF3CH2CI + 2HCI1 / CHCI = CCI 2 + 3HF> CF 3 CH 2 CI + 2HCI
2/ CF3CH2CI + HF CF3CH2F + HCI2 / CF 3 CH 2 CI + HF CF 3 CH 2 F + HCI
L'étape 1/ est réalisée en phase liquide en présence de SbC^ comme catalyseur à environ 100°C sous une pression de 15 bars.Step 1 / is carried out in the liquid phase in the presence of SbC 4 as a catalyst at approximately 100 ° C. under a pressure of 15 bars.
L'étape 2/ est réalisée en phase vapeur à 350°C sous 15 bars en présence d'un catalyseur Ni/Cr sur alumine.Step 2 / is carried out in the vapor phase at 350 ° C. at 15 bars in the presence of a Ni / Cr catalyst on alumina.
On n'observe aucune baisse de l'activité des catalyseurs après 30 jours de fonctionnement. No decrease in the activity of the catalysts is observed after 30 days of operation.

Claims

REVENDICATIONS* * * * * * * CLAIMS * * * * * * *
1. Utilisation d'une composition à base de trichloroethylene (TRI) stabilisé comme matière première, caractérisée en ce que ladite composition est constituée par du trichloroethylene, par au moins une aminé aliphatique utilisée en des quantités pondérales telles que la teneur en azote total est inférieure ou égale à 3 ppm et par au moins un phénol utilisé en des quantités pondérales au moins égales à 3 ppm et, de préférence, comprises entre 5 ppm et 10 ppm.1. Use of a composition based on trichlorethylene (TRI) stabilized as raw material, characterized in that said composition consists of trichlorethylene, by at least one aliphatic amine used in amounts by weight such that the total nitrogen content is less than or equal to 3 ppm and with at least one phenol used in weight amounts at least equal to 3 ppm and, preferably, between 5 ppm and 10 ppm.
2. Utilisation selon la revendication 1, caractérisée en ce que la teneur en azote total est comprise entre 1 ppm et 2,5 ppm.2. Use according to claim 1, characterized in that the total nitrogen content is between 1 ppm and 2.5 ppm.
3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que l'aminé aliphatique est la trieéthylamine, la diéthylamine, la diisopropylamine, la triisopropylamine, la diisobutylamine.3. Use according to claim 1 or 2, characterized in that the aliphatic amine is trieethylamine, diethylamine, diisopropylamine, triisopropylamine, diisobutylamine.
4. Utilisation selon la revendication 3, caractérisée en ce que l'aminé aliphatique est la diisopropylamine.4. Use according to claim 3, characterized in that the aliphatic amine is diisopropylamine.
5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que le phénol est le thymol.5. Use according to any one of claims 1 to 4, characterized in that the phenol is thymol.
6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que l'on utilise une quantité pondérale d'aminé aliphatique qui permet d'obtenir une teneur pondérale en azote inférieur ou égale à 3 ppm.6. Use according to any one of claims 1 to 5, characterized in that one uses a weight amount of aliphatic amine which makes it possible to obtain a weight content of nitrogen less than or equal to 3 ppm.
7. Utilisation de la composition à base de trichloroethylene stabilisé selon l'une des revendications 1 à 6 comme matière première pour la synthèse des hydrofluoroalcanes (HFA).7. Use of the composition based on stabilized trichlorethylene according to one of claims 1 to 6 as a raw material for the synthesis of hydrofluoroalkanes (HFA).
8. Utilisation de la composition selon la revendication 7 pour la synthèse du 1,1,1,2-tétrafluoroéthane (134a). 8. Use of the composition according to claim 7 for the synthesis of 1,1,1,2-tetrafluoroethane (134a).
PCT/FR2003/000306 2002-02-11 2003-01-31 Composition based on stabilized trichloroethylene used as a starting material WO2003068717A1 (en)

Priority Applications (2)

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AU2003222350A AU2003222350A1 (en) 2002-02-11 2003-01-31 Composition based on stabilized trichloroethylene used as a starting material
EP03717365A EP1476412A1 (en) 2002-02-11 2003-01-31 Composition based on stabilized trichloroethylene used as a starting material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0201613A FR2835830A1 (en) 2002-02-11 2002-02-11 COMPOSITION BASED ON STABILIZED TRICHLOROETHYLENE USABLE AS RAW MATERIAL
FR02/01613 2002-02-11

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2155723A (en) * 1937-03-08 1939-04-25 Du Pont Stabilization of trichlorethylene
FR2119014A1 (en) * 1970-12-23 1972-08-04 Central Glass Co Ltd
DE2719021A1 (en) * 1977-04-28 1978-11-09 Bayer Ag 1,1,1-Tri:fluoro-2-chloro-ethane prodn. - from tri:chloro-ethylene and hydrogen fluoride using arsenic or antimony cpd. catalyst
FR2388785A1 (en) * 1977-04-28 1978-11-24 Bayer Ag PROCESS FOR PREPARING 1,1,1-TRIFLUORO-2-CHLOROETHANE

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2155723A (en) * 1937-03-08 1939-04-25 Du Pont Stabilization of trichlorethylene
FR2119014A1 (en) * 1970-12-23 1972-08-04 Central Glass Co Ltd
DE2719021A1 (en) * 1977-04-28 1978-11-09 Bayer Ag 1,1,1-Tri:fluoro-2-chloro-ethane prodn. - from tri:chloro-ethylene and hydrogen fluoride using arsenic or antimony cpd. catalyst
FR2388785A1 (en) * 1977-04-28 1978-11-24 Bayer Ag PROCESS FOR PREPARING 1,1,1-TRIFLUORO-2-CHLOROETHANE

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 74, no. 23, 7 June 1971, Columbus, Ohio, US; abstract no. 124761, NAGAI E. ET AL: "Stabilizing trichloroethylene" XP002215685 *

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FR2835830A1 (en) 2003-08-15
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