WO1999023052A1 - Method for making an organic compound - Google Patents

Method for making an organic compound Download PDF

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Publication number
WO1999023052A1
WO1999023052A1 PCT/EP1998/007001 EP9807001W WO9923052A1 WO 1999023052 A1 WO1999023052 A1 WO 1999023052A1 EP 9807001 W EP9807001 W EP 9807001W WO 9923052 A1 WO9923052 A1 WO 9923052A1
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WIPO (PCT)
Prior art keywords
products
process according
extraction solvent
efifluent
oxirane
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PCT/EP1998/007001
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French (fr)
Inventor
Patrick Gilbeau
Original Assignee
Solvay (Societe Anonyme)
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Priority to AU20482/99A priority Critical patent/AU2048299A/en
Publication of WO1999023052A1 publication Critical patent/WO1999023052A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/32—Separation; Purification

Definitions

  • the present invention relates to a process for manufacturing an organic compound, more particularly to a process for treating the effluents obtained after the separation of the organic compound from the reaction medium.
  • the mixture of reaction products obtained at the outlet of the epoxidation reactor contains oxirane, water, various reaction by-products and possibly unconverted reagents as well as, most often, a diluent.
  • a diluent e.g. methanol or acetone.
  • the by-products are products which are formed by reaction between oxirane and water or possibly the diluent.
  • epichlorohydrin and water can form, under the usual epoxidation conditions, significant amounts of l-chloro-3-methoxy-2-propanol, l-chloro-2-methoxy-3-propanol, l, 3-dichloro-2-propanol, 2,3-dichloropropanol and l-chloro-2,3-dihydroxy-propane.
  • propylene the formation of propylene glycol as well as 1-methoxy-2-propanol and 2-methoxy-1-propanol is observed.
  • the subject of the invention is a simple process for manufacturing an organic compound in a liquid medium containing water, which makes it possible to eliminate the water-soluble by-products easily and with high efficiency and thus reduce rejection problems.
  • the invention therefore relates to a process for manufacturing an organic compound in a liquid medium containing water, according to which a mixture of reaction products comprising the organic compound, water and by-products is collected, separates at least part of the organic compound from the reaction product mixture, an effluent containing water and by-products is collected, and the efifluent is brought into contact with an extraction solvent so as to obtain two liquid phases separate.
  • the process according to the invention is very suitable when the by-products contain one or more hydrophilic groups. It is particularly suitable when the by-products contain one or more hydroxyl groups. They are most often hydroxylated compounds formed by opening the epoxide ring. The best results are obtained when the by-products additionally contain one or more halogen groups.
  • the method is particularly applicable for removing by-products such as diols and / or their monoalkether derivatives. The method according to the invention applies particularly well to the manufacture of an oxirane.
  • an olefinic compound is reacted with a peroxide compound in a liquid medium containing water, a mixture of reaction products is collected comprising oxirane, water and by-products, at least one separates part of the oxirane produced from the mixture of reaction products, an effluent containing water and by-products is collected, and the effluent is brought into contact with an extraction solvent so as to obtain two distinct liquid phases .
  • the extraction solvent can contain one or more compounds. Generally, an extraction solvent is used which has very low miscibility with water. Advantageously, the extraction solvent is such that the solubility of the above-mentioned by-products is higher in the extraction solvent than in water.
  • Extraction solvents are usually used, the boiling point of which differs from that of the by-products by at least 5 ° C, in particular by at least 10 ° C. The best results are obtained when these boiling points differ by at least 15 ° C. It is preferred to use extraction solvents with a higher boiling point than that of the by-products.
  • the boiling point of the solvent is at least 5 ° C, in particular at least 10 ° C, more particularly at least 20 ° C higher than that of the by-products. Differences of at least 50 ° C may also be suitable.
  • Compounds which can be used as extraction solvent in the process according to the invention are the aliphatic or aromatic organic derivatives which can include sulfur, phosphorus, nitrogen, oxygen and / or halogen atoms.
  • Trialkylphoshpine-oxides in which each of the alkyl groups contains from 2 to 20 carbon atoms, in particular from 4 to 10 carbon atoms, are very suitable.
  • Trihexylphosphine-oxide Trihexylphosphine-oxide, trioctylphosphine-oxide, (octyl, dihexyl) phosphine-oxide, (hexyl, dioctyl) phosphine-oxide and mixtures thereof are particularly preferred.
  • the contact between the extraction solvent and the efifluent can be carried out according to the conventional liquid-liquid extraction methods.
  • the temperature at which the extraction solvent and the efifluent are brought into contact depends on the melting point of the extraction solvent and is generally such that the extraction solvent is liquid. In practice, the temperature can vary from 0 to 95 ° C, in particular from 50 to 90 ° C.
  • the contacting of the extraction solvent with the efifluent is generally carried out at a pressure which can vary from a subatmospheric pressure to 30 bars.
  • the pressure is advantageously at least equal to atmospheric pressure and at most 20 bars.
  • the weight ratio between the extraction solvent and the efifluent depends on the solvent used and the extraction equipment used. In practice, the weight ratio between the extraction solvent and the efifluent is generally at least 0.1. Preferably, it is at least 1. This ratio does not usually exceed 20. Most often, it does not exceed 5. Good results have been obtained with a ratio of 1 to 5.
  • the efifluent generally contains at least 1% by weight of by-products, in particular at least 5% by weight. Most often, the efifluent contains at least 10% by weight of by-products. The concentration of by-products does not generally exceed 50% by weight of the efifluent, in particular not 30% by weight. The efifluent most often contains less than 20% by weight of by-products.
  • the duration of the contact of the extraction solvent with the efifluent is not critical. It can vary from 10 to 60 min. It is for example equal to approximately 30 min.
  • the oxirane which can be prepared by the process according to the invention is an organic compound corresponding to the general formula:
  • Oxirane generally contains from 2 to 20 carbon atoms, preferably from 3 to 10 carbon atoms. It may contain halogen atoms, in particular chlorine.
  • An olefinic compound which is very suitable in the process according to the invention is allyl chloride.
  • the olefinic compounds can also be chosen from alpha-olefins. Mention may be made, by way of examples, of propylene, 1-octene and 1-decene. Propylene works well.
  • An oxirane which can be advantageously prepared by the process according to the invention is epichlorohydrin. Propylene oxide can also be made.
  • the peroxide compound which can be used in the process according to the invention can be chosen from hydrogen peroxide and any peroxide compound containing active oxygen and capable of carrying out an epoxidation, preferably with the exception of hydroperoxide . Mention may be made, by way of examples, of the perxoydated compounds obtained by oxidation of organic compounds such as ethylbenzene, isobutane and isopropanol. Hydrogen peroxide is preferred.
  • the step of separating at least part of the organic compound from the mixture of reaction products can be carried out by bringing this mixture into contact with an organic extraction liquid so as to obtain two distinct liquid phases, namely, on the one hand, an organic extract containing the majority of the quantity of organic compound produced, and, on the other hand, an aqueous raffinate containing water and water soluble by-products.
  • the efifluent collected at the end of the step of separating at least part of the organic compound from the mixture of reaction products can be subjected to a distillation step before it is brought into contact with the extraction solvent. This is particularly advantageous when a hydroxyl diluent is used in the manufacture of the organic compound. A large part of the hydroxyl diluent is found in the efifluent. The hydroxyl diluent can then be separated in the distillation step and recycled in the manufacture of the organic compound.
  • the process according to the invention it is possible to collect, after extraction of the efifluent, on the one hand, a first liquid phase containing the extraction solvent and the by-products and, on the other hand, a liquid phase containing the water. Then, the first liquid phase can be subjected to vacuum evaporation in order to recover the extraction solvent in the purified state. The purified extraction solvent can then be recycled in the process according to the invention.
  • Table 1 shows the extraction rate obtained for each by-product.
  • the extraction rate is the ratio between the weight of the by-product in question present in the extract and the weight of this by-product present in the efifluent before extraction.
  • Example 2 The effluent of Example 1 was brought into contact with a mixture of alkylphosphines-oxide, the alkyl chains of which are hexyl or octyl groups, at 60 ° C., for 30 min and at atmospheric pressure.
  • the extraction rates are collated in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Removal Of Specific Substances (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

The invention concerns a method for making an organic compound in a liquid medium containing water, which consists in collecting a mixture of reaction products comprising the organic compound, water and by-products; separating at least part of the organic compound from the mixture of reaction products; collecting an effluent containing water and the by-products, and contacting the effluent with an extraction solvent to obtain two separate liquid phases.

Description

Procédé de fabrication d'un composé organique Method of manufacturing an organic compound
La présente invention se rapporte à un procédé de fabrication d'un composé organique, plus particulièrement à un procédé de traitement des effluents obtenus après la séparation du composé organique du milieu réactionnel.The present invention relates to a process for manufacturing an organic compound, more particularly to a process for treating the effluents obtained after the separation of the organic compound from the reaction medium.
Il est connu, notamment par la demande de brevet EP-A-100119, de transformer un composé oléfinique (c'est-à-dire un composé organique comportant au moins une double liaison carbone-carbone) en l'oxiranne correspondant par réaction avec du peroxyde d'hydrogène dans un milieu liquide contenant de l'eau. Ce procédé permet par exemple de synthétiser du 1,2- époxypropane (oxyde de propylène) ou du l,2-époxy-3-chloropropane (épichlorhydrine) au départ, respectivement, de propylène ou de chlorure d'allyle. Dans ce procédé connu, le mélange de produits réactionnels obtenu à la sortie du réacteur d'époxydation contient l'oxiranne, de l'eau, divers sous- produits de réaction et éventuellement des réactifs non convertis ainsi que, le plus souvent, un diluant (par exemple du méthanol ou de l'acétone). Parmi les sous- produits, on retrouve des produits qui sont formés par réaction entre l'oxiranne et de l'eau ou éventuellement le diluant. Par exemple, lorsque ce procédé est appliqué à la synthèse d' épichlorhydrine par réaction entre du chlorure d'allyle et du peroxyde d'hydrogène dans du méthanol et de l'eau, l' épichlorhydrine et l'eau (ou le méthanol) peuvent former, dans les conditions habituelles d'époxydation, des quantités notables de l-chloro-3-méthoxy-2-propanol, de l-chloro-2- méthoxy-3-propanol, de l,3-dichloro-2-propanol, de 2,3-dichloropropanol et de l-chloro-2,3-dihydroxy-propane. Au départ de propylène, on observe la formation de propylène glycol ainsi que de l-méthoxy-2-propanol et de 2- méthoxy-1-propanol. Ces sous-produits sont solubles dans l'eau et se retrouvent dès lors dans l' effiuent aqueux qui est receuilli après la séparation de l'oxiranne du milieu réactionnel. Certains des sous-produits solubles dans l'eau (en particulier le l-chloro-3-méthoxy-2-propanol et le l,3-dichloro-2-propanol) forment des azéotropes avec l'eau. On ne peut par conséquent pas les séparer aisément par distillation ou par stripping. En outre, ces sous-produits posent des problèmes de rejet car ils contribuent à la demande chimique en oxygène et, le cas échéant, à la présence de composés halogènes indésirables. L'invention a pour objet un procédé simple de fabrication d'un composé organique dans un milieu liquide contenant de l'eau, qui permette d'éliminer les sous-produits solubles dans l'eau de manière aisée et avec une efficacité élevée et de réduire ainsi les problèmes de rejet. L'invention concerne dès lors un procédé de fabrication d'un composé organique dans un milieu liquide contenant de l'eau, selon lequel on recueille un mélange de produits réactionnels comprenant le composé organique, de l'eau et des sous-produits, on sépare au moins une partie du composé organique du mélange de produits réactionnels, on recueille un effiuent contenant de l'eau et des sous-produits, et on met l'efifluent en contact avec un solvant d'extraction de manière à obtenir deux phases liquides distinctes.It is known, in particular from patent application EP-A-100119, to transform an olefinic compound (that is to say an organic compound comprising at least one carbon-carbon double bond) into the corresponding oxirane by reaction with hydrogen peroxide in a liquid medium containing water. This process makes it possible, for example, to synthesize 1,2-epoxypropane (propylene oxide) or 1,2-epoxy-3-chloropropane (epichlorohydrin) starting, respectively, from propylene or allyl chloride. In this known process, the mixture of reaction products obtained at the outlet of the epoxidation reactor contains oxirane, water, various reaction by-products and possibly unconverted reagents as well as, most often, a diluent. (e.g. methanol or acetone). Among the by-products are products which are formed by reaction between oxirane and water or possibly the diluent. For example, when this process is applied to the synthesis of epichlorohydrin by reaction between allyl chloride and hydrogen peroxide in methanol and water, epichlorohydrin and water (or methanol) can form, under the usual epoxidation conditions, significant amounts of l-chloro-3-methoxy-2-propanol, l-chloro-2-methoxy-3-propanol, l, 3-dichloro-2-propanol, 2,3-dichloropropanol and l-chloro-2,3-dihydroxy-propane. Starting from propylene, the formation of propylene glycol as well as 1-methoxy-2-propanol and 2-methoxy-1-propanol is observed. These by-products are soluble in water and are therefore found in the aqueous effluent which is collected after the separation of the oxirane from the reaction medium. Some of the water-soluble byproducts (in particular l-chloro-3-methoxy-2-propanol and l, 3-dichloro-2-propanol) form azeotropes with water. They cannot therefore be easily separated by distillation or stripping. In addition, these by-products pose rejection problems because they contribute to the chemical oxygen demand and, where appropriate, to the presence of undesirable halogenated compounds. The subject of the invention is a simple process for manufacturing an organic compound in a liquid medium containing water, which makes it possible to eliminate the water-soluble by-products easily and with high efficiency and thus reduce rejection problems. The invention therefore relates to a process for manufacturing an organic compound in a liquid medium containing water, according to which a mixture of reaction products comprising the organic compound, water and by-products is collected, separates at least part of the organic compound from the reaction product mixture, an effluent containing water and by-products is collected, and the efifluent is brought into contact with an extraction solvent so as to obtain two liquid phases separate.
Le procédé selon l'invention convient bien lorsque les sous-produits contiennent un ou plusieurs groupements hydrophiles. Il convient particulièrement bien lorsque les sous-produits contiennent un ou plusieurs groupements hydroxyle. Il s'agit le plus souvent de composés hydroxylés formés par ouverture du cycle époxyde. Les meilleurs résultats sont obtenus lorsque les sous-produits contiennent en outre un ou plusieurs groupements halogènes. Le procédé s'applique particulièrement bien pour éliminer des sous-produits tels que des diols et/ou leurs dérivés monoalk léthers. Le procédé selon l'invention s'applique particulièrement bien à la fabrication d'un oxiranne. Dans ce cas, on fait réagir un composé oléfinique avec un composé peroxyde dans un milieu liquide contenant de l'eau, on recueille un mélange de produits réactionnels comprenant l'oxiranne, de l'eau et des sous-produits, on sépare au moins une partie de l'oxiranne produit du mélange de produits réactionnels, on recueille un effiuent contenant de l'eau et des sous-produits, et on met l'effluent en contact avec un solvant d'extraction de manière à obtenir deux phases liquides distinctes.The process according to the invention is very suitable when the by-products contain one or more hydrophilic groups. It is particularly suitable when the by-products contain one or more hydroxyl groups. They are most often hydroxylated compounds formed by opening the epoxide ring. The best results are obtained when the by-products additionally contain one or more halogen groups. The method is particularly applicable for removing by-products such as diols and / or their monoalkether derivatives. The method according to the invention applies particularly well to the manufacture of an oxirane. In this case, an olefinic compound is reacted with a peroxide compound in a liquid medium containing water, a mixture of reaction products is collected comprising oxirane, water and by-products, at least one separates part of the oxirane produced from the mixture of reaction products, an effluent containing water and by-products is collected, and the effluent is brought into contact with an extraction solvent so as to obtain two distinct liquid phases .
Le solvant d'extraction peut contenir un ou plusieurs composés. Généralement, on utilise un solvant d'extraction qui présente une miscibilité très faible avec l'eau. Avantageusement, le solvant d'extraction est tel que la solubilité des sous-produits précités soit plus élevée dans le solvant d'extraction que dans l'eau. Un solvant d'extraction substantiellement stable et inerte chimiquement vis- à-vis des constituants de l'efifluent aqueux dans les conditions d'extraction, ainsi que, le cas échéant, dans les étapes ultérieures convient particulièrement bien. Des solvants d'extraction qui donnent de bons résultats sont ceux dont le poids spécifique diffère de celui de l'efifluent d'au moins 0,02 g/cm^, en particulier d'au moins 0,04 g/cmJ. Les meilleurs résultats sont obtenus lorsque ces poids spécifiques diffèrent d'au moins 0,05 g/cmThe extraction solvent can contain one or more compounds. Generally, an extraction solvent is used which has very low miscibility with water. Advantageously, the extraction solvent is such that the solubility of the above-mentioned by-products is higher in the extraction solvent than in water. An extraction solvent which is substantially stable and chemically inert with respect to the constituents of the aqueous efifluent under the extraction conditions, as well as, where appropriate, in the subsequent stages, is particularly suitable. Extraction solvents which give good results are those whose specific gravity differs from that of the efifluent by at least 0.02 g / cm ^, in particular at least 0.04 g / cm J. The best results are obtained when these specific weights differ by at least 0.05 g / cm
Il peut s'avérer intéressant d'utiliser un solvant d'extraction dont le point d'ébullition est élevé par rapport aux sous-produits précités. Ceci permet en effet de séparer les sous-produits du solvant d'extraction dans un évaporateur sans devoir distiller le solvant d'extraction, de purifier ainsi le solvant d'extraction et de le recycler dans le procédé selon l'invention. On utilise habituellement des solvants d'extraction dont le point d'ébullition diffère de celui des sous-produits d'au moins 5 °C, en particulier d'au moins 10 °C. Les meilleurs résultats sont obtenus lorsque ces points d'ébullition diffèrent d'au moins 15 °C. On préfère utiliser des solvants d'extraction dont le point d'ébullition est plus élevé que celui des sous-produits. Par exemple, le point d'ébullition du solvant est d'au moins 5 °C, en particulier d'au moins 10 °C, plus particulièrement d'au moins 20 °C supérieur à celui des sous-produits. Des différences d'au moins 50 °C peuvent également convenir.It may be advantageous to use an extraction solvent whose boiling point is high compared to the aforementioned by-products. This in fact makes it possible to separate the by-products from the extraction solvent in an evaporator without having to distill the extraction solvent, thereby purifying the extraction solvent and recycling it in the process according to the invention. Extraction solvents are usually used, the boiling point of which differs from that of the by-products by at least 5 ° C, in particular by at least 10 ° C. The best results are obtained when these boiling points differ by at least 15 ° C. It is preferred to use extraction solvents with a higher boiling point than that of the by-products. For example, the boiling point of the solvent is at least 5 ° C, in particular at least 10 ° C, more particularly at least 20 ° C higher than that of the by-products. Differences of at least 50 ° C may also be suitable.
Des composés qui peuvent être utilisés comme solvant d'extraction dans le procédé selon l'invention sont les dérivés organiques aliphatiques ou aromatiques pouvant inclure des atomes de soufre, phosphore, azote, oxygène et/ou halogène. On peut citer à titre d'exemples les trialkylphosphines-oxyde et le 1,2- dichloropropane. Ce dernier s'avère tout particulièrement intéressant lorsque l'on souhaite fabriquer l'épichlorydrine car il est formé comme sous-produit dans la synthèse d'épichlorhydrine. Les trialkylphoshpines-oxyde dont chacun des groupes alkyle contient de 2 à 20 atomes de carbone, en particulier de 4 à 10 atomes de carbone, conviennent bien. Le trihexylphosphine-oxyde, la trioctylphosphine-oxyde, la (octyl, dihexyl) phosphine-oxyde, la (hexyl, dioctyl) phosphine-oxyde et leurs mélanges sont particulièrement préférées.Compounds which can be used as extraction solvent in the process according to the invention are the aliphatic or aromatic organic derivatives which can include sulfur, phosphorus, nitrogen, oxygen and / or halogen atoms. Examples of trialkylphosphines-oxide and 1,2-dichloropropane that may be mentioned. The latter proves to be particularly advantageous when it is desired to manufacture epichlorydrine because it is formed as a by-product in the synthesis of epichlorohydrin. Trialkylphoshpine-oxides in which each of the alkyl groups contains from 2 to 20 carbon atoms, in particular from 4 to 10 carbon atoms, are very suitable. Trihexylphosphine-oxide, trioctylphosphine-oxide, (octyl, dihexyl) phosphine-oxide, (hexyl, dioctyl) phosphine-oxide and mixtures thereof are particularly preferred.
La mise en contact entre le solvant d'extraction et l'efifluent peut être effectuée selon les méthodes classiques d'extraction liquide-liquide.The contact between the extraction solvent and the efifluent can be carried out according to the conventional liquid-liquid extraction methods.
La température à laquelle on met en contact le solvant d'extraction et l'efifluent dépend du point de fusion du solvant d'extraction et est généralement telle que le solvant d'extraction soit liquide. En pratique, la température peut varier de 0 à 95 °C, en particulier de 50 à 90 °C.The temperature at which the extraction solvent and the efifluent are brought into contact depends on the melting point of the extraction solvent and is generally such that the extraction solvent is liquid. In practice, the temperature can vary from 0 to 95 ° C, in particular from 50 to 90 ° C.
La mise en contact du solvant d'extraction avec l'efifluent est généralement réalisée à une pression qui peut varier d'une pression subatmosphérique à 30 bars. La pression est avantageusement au moins égale à la pression atmosphérique et au maximum de 20 bars. Le rapport pondéral entre le solvant d'extraction et l'efifluent dépend du solvant mis en oeuvre et de l'appareillage d'extraction utilisé. En pratique, le rapport pondéral entre le solvant d'extraction et l'efifluent est généralement d'au moins 0,1. De préférence, il est d'au moins 1. Ce rapport ne dépasse pas habituellement 20. Le plus souvent, il ne dépasse pas 5. De bons résultats ont été obtenus avec un rapport de 1 à 5.The contacting of the extraction solvent with the efifluent is generally carried out at a pressure which can vary from a subatmospheric pressure to 30 bars. The pressure is advantageously at least equal to atmospheric pressure and at most 20 bars. The weight ratio between the extraction solvent and the efifluent depends on the solvent used and the extraction equipment used. In practice, the weight ratio between the extraction solvent and the efifluent is generally at least 0.1. Preferably, it is at least 1. This ratio does not usually exceed 20. Most often, it does not exceed 5. Good results have been obtained with a ratio of 1 to 5.
L'efifluent contient généralement au moins 1 % en poids de sous-produits, en particulier au moins 5 % en poids. Le plus souvent, l'efifluent contient au moins 10 % en poids de sous-produits. La concentration en sous-produits ne dépasse pas, généralement, 50 % en poids de l'efifluent, en particulier pas 30 % en poids. L'efifluent contient le plus souvent moins de 20 % en poids de sous-produits.The efifluent generally contains at least 1% by weight of by-products, in particular at least 5% by weight. Most often, the efifluent contains at least 10% by weight of by-products. The concentration of by-products does not generally exceed 50% by weight of the efifluent, in particular not 30% by weight. The efifluent most often contains less than 20% by weight of by-products.
La durée de la mise en contact du solvant d'extraction avec l'efifluent n'est pas critique. Elle peut varier de 10 à 60 min. Elle est par exemple égale à 30 min environ. L'oxiranne qui peut être préparé par le procédé selon l'invention est un composé organique répondant à la formule générale :The duration of the contact of the extraction solvent with the efifluent is not critical. It can vary from 10 to 60 min. It is for example equal to approximately 30 min. The oxirane which can be prepared by the process according to the invention is an organic compound corresponding to the general formula:
\ /\ /
C - CCC
/ \ / \ O/ \ / \ O
L'oxiranne contient généralement de 2 à 20 atomes de carbone, de préférence de 3 à 10 atomes de carbone. Il peut renfermer des atomes d'halogène, en particulier de chlore. Un composé oléfinique qui convient bien dans le procédé selon l'invention est le chlorure d'allyle. Les composés oléfiniques peuvent également être choisis parmi les alpha-oléfines. On peut citer à titre d'exemples le propylène, le 1-octène et le 1 -décène. Le propylène convient bien. Un oxiranne qui peut être préparé de manière avantageuse par le procédé selon l'invention est l' épichlorhydrine. On peut également fabriquer de l'oxyde de propylène. Le composé peroxyde qui peut être utilisé dans le procédé selon l'invention peut être choisi parmi le peroxyde d'hydrogène et tout composé peroxyde contenant de l'oxygène actif et capable d'effectuer une époxydation, de préférence à l'exception d'hydroperoxyde. On peut citer à titre d'exemples les composés perxoydés obtenus par oxydation de composés organiques tels que l'éthylbenzène, l'isobutane et l'isopropanol. Le peroxyde d'hydrogène est préféré. Dans le procédé selon l'invention, l'étape de séparation d'au moins une partie du composé organique du mélange de produits réactionnels peut être réalisée en mettant ce mélange en contact avec un liquide organique d'extraction de manière à obtenir deux phases liquides distinctes, à savoir, d'une part, un extrait organique contenant la majorité de la quantité de composé organique produit, et, d'autre part, un raffinât aqueux contenant l'eau et les sous-produits solubles dans l'eau. Dans le procédé selon l'invention, on peut soumettre l'efifluent recueilli à l'issue de l'étape de séparation d'au moins une partie du composé organique du mélange de produits réactionnels à une étape de distillation avant sa mise en contact avec le solvant d'extraction. Ceci s'avère particulièrement intéressant lorsqu'un diluant hydroxyle est utilisé dans la fabrication du composé organique. Une grande partie du diluant hydroxyle se retrouve en effet dans l'efifluent. Le diluant hydroxyle peut alors être séparé dans l'étape de distillation et recyclé dans la fabrication du composé organique.Oxirane generally contains from 2 to 20 carbon atoms, preferably from 3 to 10 carbon atoms. It may contain halogen atoms, in particular chlorine. An olefinic compound which is very suitable in the process according to the invention is allyl chloride. The olefinic compounds can also be chosen from alpha-olefins. Mention may be made, by way of examples, of propylene, 1-octene and 1-decene. Propylene works well. An oxirane which can be advantageously prepared by the process according to the invention is epichlorohydrin. Propylene oxide can also be made. The peroxide compound which can be used in the process according to the invention can be chosen from hydrogen peroxide and any peroxide compound containing active oxygen and capable of carrying out an epoxidation, preferably with the exception of hydroperoxide . Mention may be made, by way of examples, of the perxoydated compounds obtained by oxidation of organic compounds such as ethylbenzene, isobutane and isopropanol. Hydrogen peroxide is preferred. In the process according to the invention, the step of separating at least part of the organic compound from the mixture of reaction products can be carried out by bringing this mixture into contact with an organic extraction liquid so as to obtain two distinct liquid phases, namely, on the one hand, an organic extract containing the majority of the quantity of organic compound produced, and, on the other hand, an aqueous raffinate containing water and water soluble by-products. In the process according to the invention, the efifluent collected at the end of the step of separating at least part of the organic compound from the mixture of reaction products can be subjected to a distillation step before it is brought into contact with the extraction solvent. This is particularly advantageous when a hydroxyl diluent is used in the manufacture of the organic compound. A large part of the hydroxyl diluent is found in the efifluent. The hydroxyl diluent can then be separated in the distillation step and recycled in the manufacture of the organic compound.
Dans le procédé selon l'invention, on peut recueillir après extraction de l'efifluent, d'une part, une première phase liquide contenant le solvant d'extraction et les sous-produits et, d'autre part, une phase liquide contenant de l'eau. Ensuite, on peut soumettre la première phase liquide à une évaporation sous vide afin de récupérer le solvant d'extraction à l'état épuré. On peut alors recycler le solvant d'extraction épuré dans le procédé selon l'invention.In the process according to the invention, it is possible to collect, after extraction of the efifluent, on the one hand, a first liquid phase containing the extraction solvent and the by-products and, on the other hand, a liquid phase containing the water. Then, the first liquid phase can be subjected to vacuum evaporation in order to recover the extraction solvent in the purified state. The purified extraction solvent can then be recycled in the process according to the invention.
Le procédé selon l'invention s'est révélé très avantageux pour préparer le l,2-époxy-3-chloropropane par réaction entre le chlorure d'allyle et du peroxyde d'hydrogène. Il convient également pour la préparation du 1,2-époxypropane par réaction entre le propylène et du peroxyde d'hydrogène. Exemples 1 à 3 (conformes à l'invention)The process according to the invention has proved to be very advantageous for preparing 1,2-epoxy-3-chloropropane by reaction between allyl chloride and hydrogen peroxide. It is also suitable for the preparation of 1,2-epoxypropane by reaction between propylene and hydrogen peroxide. Examples 1 to 3 (in accordance with the invention)
Un effiuent aqueux sortant de la synthèse d' épichlorhydrine au départ de chlorure d'allyle et de peroxyde d'hydrogène qui contient 70 g/kg de l-chloro-3- méthoxy-2-propanol, 3,7 g/kg de l-chloro-2-méthoxy-3-propanol, 11 g/kg de 1,3-dichloro-propanol, 0,4 g/kg de 2,3-dichloro-propanol et 73 g/kg de 1-chloro- 2,3-dihydroxy-propane a été mis en contact avec un poids égal de trioctylphosphine-oxyde à une température de 60 °C (exemple 1), 75 °C (exemple 2), 90 °C (exemple 3) pendant une durée de 30 min et à une pression atmosphérique . Deux phases liquides distinctes ont été obtenues et analysées. Le tableau 1 mentionne le taux d'extraction obtenu pour chaque sous-produit. Le taux d'extraction est le rapport entre le poids du sous-produit en question présent dans l'extrait et le poids de ce sous-produit présent dans l'efifluent avant extraction. Tableau 1 ExempleAn aqueous effluent leaving the synthesis of epichlorohydrin from allyl chloride and hydrogen peroxide which contains 70 g / kg of l-chloro-3-methoxy-2-propanol, 3.7 g / kg of l -chloro-2-methoxy-3-propanol, 11 g / kg of 1,3-dichloro-propanol, 0.4 g / kg of 2,3-dichloro-propanol and 73 g / kg of 1-chloro-2, 3-dihydroxy-propane was contacted with an equal weight of trioctylphosphine-oxide at a temperature of 60 ° C (example 1), 75 ° C (example 2), 90 ° C (example 3) for a period of 30 min and at atmospheric pressure. Two distinct liquid phases were obtained and analyzed. Table 1 shows the extraction rate obtained for each by-product. The extraction rate is the ratio between the weight of the by-product in question present in the extract and the weight of this by-product present in the efifluent before extraction. Table 1 Example
1 -chloro-3 -méthoxy-2-propanol 85 84 84 1 -chloro-2-méthoxy-3-propanol 83 82 81 1 , 3 -dichloro-propanol 98 98 97 2,3-dichloro-propanol 100 100 89 l-chloro-2,3-dihydroxy-propane 68 69 671-3-chloro-2-methoxy-propanol 85 84 84 1-2-chloro-methoxy-3-propanol 83 82 81 1, 3-dichloro-propanol 98 98 97 2,3-dichloro-propanol 100 100 89 l- chloro-2,3-dihydroxy-propane 68 69 67
Exemple 4 (conforme à l'invention)Example 4 (according to the invention)
L'efifluent de l'exemple 1 a été mis en contact avec un mélange d'alkylphosphines-oxyde dont les chaînes alkyle sont des groupes hexyle ou octyle, à 60 °C, pendant 30 min et à pression atmosphérique . Les taux d'extraction sont rassemblés dans le tableau 2.The effluent of Example 1 was brought into contact with a mixture of alkylphosphines-oxide, the alkyl chains of which are hexyl or octyl groups, at 60 ° C., for 30 min and at atmospheric pressure. The extraction rates are collated in Table 2.
Tableau 2 l-chloro-3-méthoxy-2-propanol 86 l-chloro-2-méthoxy-3-propanol 82Table 2 l-chloro-3-methoxy-2-propanol 86 l-chloro-2-methoxy-3-propanol 82
1,3 -dichloro-propanol 981,3-dichloro-propanol 98
2,3 -dichloro-propanol 100 l-chloro-2,3-dihydroxy-propane 71 2,3-dichloro-propanol 100 l-chloro-2,3-dihydroxy-propane 71

Claims

R E V E N D I C A T I O N SR E V E N D I C A T I O N S
1 - Procédé de fabrication d'un composé organique dans un milieu liquide contenant de l'eau, selon lequel on recueille un mélange de produits réactionnels comprenant le composé organique, de l'eau et des sous-produits, on sépare au moins une partie du composé organique du mélange de produits réactionnels, on recueille un effiuent contenant de l'eau et des sous-produits, et on met l'efifluent en contact avec un solvant d'extraction de manière à obtenir deux phases liquides distinctes.1 - Process for manufacturing an organic compound in a liquid medium containing water, according to which a mixture of reaction products comprising the organic compound, water and by-products is collected, at least part is separated of the organic compound of the reaction product mixture, an effluent containing water and by-products is collected, and the efifluent is brought into contact with an extraction solvent so as to obtain two distinct liquid phases.
2 - Procédé selon la revendication 1, dans lequel les sous-produits contiennent un ou plusieurs groupements hydrophiles.2 - Process according to claim 1, in which the by-products contain one or more hydrophilic groups.
3 - Procédé selon la revendication 2, dans lequel les sous-produits contiennent un ou plusieurs groupements hydroxyle.3 - Process according to claim 2, wherein the by-products contain one or more hydroxyl groups.
4 - Procédé selon la revendication 2 ou 3, dans lequel les sous-produits contiennent en outre un ou plusieurs groupements halogènes.4 - Process according to claim 2 or 3, wherein the by-products further contain one or more halogen groups.
5 - Procédé selon l'une quelconque des revendications 1 à 4 appliqué à la fabrication d'un oxiranne, selon lequel on fait réagir un composé oléfinique avec un composé peroxyde dans un milieu liquide contenant de l'eau, on recueille un mélange de produits réactionnels comprenant l'oxiranne, de l'eau et des sous- produits, on sépare au moins une partie de l'oxiranne produit du mélange de produits réactionnels, on recueille un effiuent contenant de l'eau et des sous- produits, et on met l'efifluent en contact avec un solvant d'extraction de manière à obtenir deux phases liquides distinctes.5 - Process according to any one of claims 1 to 4 applied to the manufacture of an oxirane, according to which an olefinic compound is reacted with a peroxide compound in a liquid medium containing water, a mixture of products is collected comprising oxirane, water and by-products, at least a portion of the product oxirane is separated from the mixture of reaction products, an effluent containing water and by-products is collected, and puts the efifluent in contact with an extraction solvent so as to obtain two distinct liquid phases.
6 - Procédé selon l'une quelconques des revendications 1 à 5, dans lequel le poids spécifique du solvant d'extraction diffère de celui de l'efifluent d'au moins 0,04 g/cm3.6 - Process according to any one of claims 1 to 5, wherein the specific weight of the extraction solvent differs from that of the efifluent by at least 0.04 g / cm 3 .
7 - Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le point d'ébullition du solvant d'extraction diffère de celui des sous-produits d'au moins 5 °C.7 - Process according to any one of claims 1 to 6, wherein the boiling point of the extraction solvent differs from that of the by-products by at least 5 ° C.
8 - Procédé selon l'une quelconque des revendications 1 à 7, dans lequel le solvant d'extraction est choisi parmi les dérivés organiques aliphatiques ou aromatiques pouvant inclure des atomes de soufre, phosphore, azote, oxygène et/ou halogène.8 - Process according to any one of claims 1 to 7, in which the extraction solvent is chosen from aliphatic organic derivatives or aromatics which may include sulfur, phosphorus, nitrogen, oxygen and / or halogen atoms.
9 - Procédé selon la revendication 8, dans lequel le solvant d'extraction est choisi parmi les trialkylphosphines-oxyde dont chacun des groupes alkyle contient de 2 à 20 atomes de carbone.9 - Process according to claim 8, in which the extraction solvent is chosen from trialkylphosphines-oxide in which each of the alkyl groups contains from 2 to 20 carbon atoms.
10 - Procédé selon l'une quelconque des revendications 1 à 9, dans lequel l'efifluent est mis en contact avec le solvant d'extraction dans une colonne d'extraction liquide-liquide, à une température de 50 à 95 °C.10 - Process according to any one of claims 1 to 9, wherein the efifluent is brought into contact with the extraction solvent in a liquid-liquid extraction column, at a temperature of 50 to 95 ° C.
11 - Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le rapport pondéral entre le solvant d'extraction et l'efifluent est de 0, 1 à 20.11 - Process according to any one of claims 1 to 10, in which the weight ratio between the extraction solvent and the efifluent is from 0.1 to 20.
12 - Procédé selon l'une quelconque des revendications 1 à 1 1, dans lequel on recueille après extraction de l'efifluent, d'une part, une première phase liquide contenant le solvant d'extraction et les sous-produits et, d'autre part, une phase liquide contenant de l'eau, on soumet la première phase liquide à une évaporation sous vide afin de récupérer le solvant d'extraction à l'état épuré, et on recycle le solvant d'extraction épuré.12 - Process according to any one of claims 1 to 1 1, wherein there is collected after extraction of the efifluent, on the one hand, a first liquid phase containing the extraction solvent and by-products and, on the other hand, a liquid phase containing water, the first liquid phase is subjected to vacuum evaporation in order to recover the extraction solvent in the purified state, and the purified extraction solvent is recycled.
13 - Procédé selon l'une quelconque des revendications 5 à 12, dans lequel le composé peroxyde est le peroxyde d'hydrogène, le composé oléfinique est le chlorure d'allyle et l'oxiranne est le l,2-époxy-3-chloropropane.13 - Process according to any one of claims 5 to 12, in which the peroxide compound is hydrogen peroxide, the olefinic compound is allyl chloride and the oxirane is 1,2-epoxy-3-chloropropane .
14 - Procédé selon l'une quelconque des revendications 5 à 12, dans lequel le composé peroxyde est le peroxyde d'hydrogène, le composé oléfinique est le propylène et l'oxiranne est le 1,2-epoxypropane. 14 - Process according to any one of claims 5 to 12, wherein the peroxide compound is hydrogen peroxide, the olefinic compound is propylene and the oxirane is 1,2-epoxypropane.
PCT/EP1998/007001 1997-11-05 1998-10-29 Method for making an organic compound WO1999023052A1 (en)

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