BE825563A - ETHYLPHENOL PRODUCTION PROCESS - Google Patents

ETHYLPHENOL PRODUCTION PROCESS

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Publication number
BE825563A
BE825563A BE153388A BE153388A BE825563A BE 825563 A BE825563 A BE 825563A BE 153388 A BE153388 A BE 153388A BE 153388 A BE153388 A BE 153388A BE 825563 A BE825563 A BE 825563A
Authority
BE
Belgium
Prior art keywords
emi
mixture
hydrogenation
diethylbenzene
decomposition
Prior art date
Application number
BE153388A
Other languages
French (fr)
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed filed Critical
Priority to BE153388A priority Critical patent/BE825563A/en
Publication of BE825563A publication Critical patent/BE825563A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
    • C07C409/08—Compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

       

  Procédé de production d'éthylphénols

  
La présente invention se rapporte à un procédé de production d'éthylphénols par oxydation en phase liquide de diéthylbenzènes.

  
Dans son brevet belge n[deg.] 789.653, la Demanderesse décrit un procédé qui consiste à effectuer l'oxydation de diéthylbenzène en mettant ce dernier en contact

  
 <EMI ID=1.1>   <EMI ID=2.1> 
 <EMI ID=3.1> 
 <EMI ID=4.1> 

  

 <EMI ID=5.1> 


  
Mais pendant ce procédé, il se forme des sous-produits qui exercent une

  
 <EMI ID=6.1> 

  

 <EMI ID=7.1> 


  
 <EMI ID=8.1>   <EMI ID=9.1> 

  
mélange contenant moins d'impuretés,

  
 <EMI ID=10.1> 

  
concentrât avec un solvant choisi parmi les alcools et les cétones aliphatiques

  
à bas poids moléculaire, puis décomposition de l'hydroperoxyde par contact intime avec un acide fort, est caractérise en ce qu'on effectue l'hydrogénation du  mélange résultant de cette décomposition, puis on récupère l'éthylphénol hors du

  
 <EMI ID=11.1> 

  

 <EMI ID=12.1> 


  
 <EMI ID=13.1> 
 <EMI ID=14.1> 
 
 <EMI ID=15.1> 
 <EMI ID=16.1> 

  
Certains sous-produits se forment aussi pendant la réaction de décomposi-

  
 <EMI ID=17.1> 

  
se forment probablement en même temps que l'éthylphénol quand le monohydroperoxyde de diéthylbenzène est décomposé par l'acide fort, ainsi qu'en acétylphénol qui est

  
 <EMI ID=18.1> 

  
En effectuant l'hydrogénation du mélange de décomposition, les groupes

  
 <EMI ID=19.1> 

  
 <EMI ID=20.1> 

  
Il est inattendu que les sous-produits ci-dessus puissent être hydrogénés en produits valables. En effet, lors de la production de phénol et d'acétone par

  
 <EMI ID=21.1> 

  
contenant le phénol, l'acétone et ces sous-produits, seul l'alpha-méthylstyrène est hydrogéné en cumins (brevet américain n[deg.] 3.436.429).

  
L'étape d'hydrogénation suivant l'invention peut être appliquée directement sur le mélange de réaction acide obtenu après décomposition du concentrât de

  
 <EMI ID=22.1>   <EMI ID=23.1> 

  
Les conditions de réaction (type et quantité de catalyseur, température,

  
 <EMI ID=24.1> 

  
hydrogénation du noyau benzénique, sans hydrogénolyse du groupe hydroxyle phénolique, et sans hydrogénation de l'acétaldéhyde et du solvant mélangés au concentrat de monohydroperoxyde.

  
D'après un mode d'exécution de l'invention, l'hydrogénation est appliquée au mélange de décomposition acide contenant l'acétaldéhyde et le solvant. Dana ce mode d'exécution, on effectue l'hydrogénation de préférence en présence d'un catalyseur au palladium, éventuellement sur un support tel qu'alumine ou charbon actif.

  
D'après un autre mode d'exécution de l'invention, le mélange de décomposition., après avoir été éventuellement neutralisa, est distillé pour enlever

  
 <EMI ID=25.1> 

  
solvant. On effectue ensuite une distillation éclair pour enlever les sels et les goudrons. Le mélange résultant, contenant le diéthylbenzène, l'éthylphénol,

  
 <EMI ID=26.1> 

  
facilement séparés par distillation à pression atmosphérique. On peut effectuer l'hydrogénation en une seule étape ou en plusieurs étapes, par exemple avec élévation progressive de la température. Les catalyseurs qui conviennent pour l'hydrogénation sont à base de métaux de transition des groupes VI à VIII, éventuellement sur un support, et particulièrement le platine et le palladium et leurs

  
 <EMI ID=27.1>  

  
 <EMI ID=28.1> 

  
Les exemples suivants sont- donnés- titre d'illustration et ne comportent aucun caractère limitatif.

  
 <EMI ID=29.1> 

  
 <EMI ID=30.1> 

  
 <EMI ID=31.1> 

  
distillé, On a fait barbotter de l'air dans le liquide, tout en agitant et on a

  
 <EMI ID=32.1> 

  
On a ensuite diminué le pourcentage d'oxygène dans le gaz d'échappement pour

  
 <EMI ID=33.1> 

  
 <EMI ID=34.1> 

  
 <EMI ID=35.1> 

  
 <EMI ID=36.1> 

  
at sous 2 mm. Hg., la majeure partie du diéthylbenzène non transformé. 100 g de concentrât d'hydroperoxydes contenait
 <EMI ID=37.1> 
 
 <EMI ID=38.1> 
 <EMI ID=39.1> 

  
et une partie de l'acétaldéhyde formé.

  
On a refroidi à 20[deg.]C et on a divisé le mélange en deux parties égales.

  
L'analyse d'une de ces parties a montré que 99 % des hydroperoxydes

  
 <EMI ID=40.1> 

  

 <EMI ID=41.1> 


  
 <EMI ID=42.1> 

  
On a ajouté 1,5 g. de palladium sur charbon actif (catalyseur contenant 5 % de palladium) à l'autre partie du mélange réactionnel et on a introduit dans un autoclave. On a effectué l'hydrogénation à 10 atm., le mélange de réaction

  
 <EMI ID=43.1> 

  
de l'absorption d'hydrogène.

  
On a ensuite relâché la pression, on a refroidi le mélange réactionnel et on l'a soutiré. L'analyse a montré que ce mélange était exempt d'éthylacéto-

  
 <EMI ID=44.1>   <EMI ID=45.1> 

Exemple 2.

  
 <EMI ID=46.1> 

  
 <EMI ID=47.1> 

  
par de l'acide sulfurique en présence d'acétone.

  
Le mélange réactionnel a été neutralisé par une solution aqueuse de

  
 <EMI ID=48.1> 

  
 <EMI ID=49.1> 

  
 <EMI ID=50.1> 

  

 <EMI ID=51.1> 


  
On a introduit ce mélange dans un autoclave en acier inoxydable 316

  
 <EMI ID=52.1> 

  
préalablement activé. On a traité par de l'hydrogène à 130[deg.]C et sous une pression

  
 <EMI ID=53.1> 

  
catalyseur et on a obtenu un mélange B contenant :

  

 <EMI ID=54.1> 




  Ethylphenol production process

  
The present invention relates to a process for the production of ethylphenols by liquid phase oxidation of diethylbenzenes.

  
In its Belgian patent n [deg.] 789,653, the Applicant describes a process which consists in carrying out the oxidation of diethylbenzene by bringing the latter into contact.

  
 <EMI ID = 1.1> <EMI ID = 2.1>
 <EMI ID = 3.1>
 <EMI ID = 4.1>

  

 <EMI ID = 5.1>


  
But during this process, by-products are formed which exert a

  
 <EMI ID = 6.1>

  

 <EMI ID = 7.1>


  
 <EMI ID = 8.1> <EMI ID = 9.1>

  
mixture containing less impurities,

  
 <EMI ID = 10.1>

  
concentrate with a solvent chosen from alcohols and aliphatic ketones

  
at low molecular weight, then decomposition of the hydroperoxide by intimate contact with a strong acid, is characterized in that the hydrogenation of the mixture resulting from this decomposition is carried out, then the ethylphenol is recovered from the

  
 <EMI ID = 11.1>

  

 <EMI ID = 12.1>


  
 <EMI ID = 13.1>
 <EMI ID = 14.1>
 
 <EMI ID = 15.1>
 <EMI ID = 16.1>

  
Certain by-products are also formed during the decomposition reaction.

  
 <EMI ID = 17.1>

  
probably form together with ethylphenol when diethylbenzene monohydroperoxide is broken down by strong acid, as well as acetylphenol which is

  
 <EMI ID = 18.1>

  
By carrying out the hydrogenation of the decomposition mixture, the groups

  
 <EMI ID = 19.1>

  
 <EMI ID = 20.1>

  
It is unexpected that the above by-products could be hydrogenated into valuable products. Indeed, during the production of phenol and acetone by

  
 <EMI ID = 21.1>

  
containing phenol, acetone and these by-products, only alpha-methylstyrene is hydrogenated to cumins (US patent no. [deg.] 3,436,429).

  
The hydrogenation step according to the invention can be applied directly to the acid reaction mixture obtained after decomposition of the concentrate of

  
 <EMI ID = 22.1> <EMI ID = 23.1>

  
The reaction conditions (type and quantity of catalyst, temperature,

  
 <EMI ID = 24.1>

  
hydrogenation of the benzene ring, without hydrogenolysis of the phenolic hydroxyl group, and without hydrogenation of acetaldehyde and solvent mixed with the monohydroperoxide concentrate.

  
According to one embodiment of the invention, the hydrogenation is applied to the acidic decomposition mixture containing the acetaldehyde and the solvent. In this embodiment, the hydrogenation is preferably carried out in the presence of a palladium catalyst, optionally on a support such as alumina or activated carbon.

  
According to another embodiment of the invention, the decomposition mixture, after having been optionally neutralized, is distilled to remove

  
 <EMI ID = 25.1>

  
solvent. A flash distillation is then carried out to remove salts and tars. The resulting mixture, containing diethylbenzene, ethylphenol,

  
 <EMI ID = 26.1>

  
easily separated by distillation at atmospheric pressure. The hydrogenation can be carried out in a single step or in several steps, for example with a gradual rise in temperature. The catalysts which are suitable for the hydrogenation are based on transition metals from groups VI to VIII, optionally on a support, and particularly platinum and palladium and their

  
 <EMI ID = 27.1>

  
 <EMI ID = 28.1>

  
The following examples are given by way of illustration and are in no way limiting.

  
 <EMI ID = 29.1>

  
 <EMI ID = 30.1>

  
 <EMI ID = 31.1>

  
distilled, air was bubbled through the liquid while stirring and

  
 <EMI ID = 32.1>

  
The percentage of oxygen in the exhaust gas was then reduced to

  
 <EMI ID = 33.1>

  
 <EMI ID = 34.1>

  
 <EMI ID = 35.1>

  
 <EMI ID = 36.1>

  
at under 2 mm. Hg., Most of the unconverted diethylbenzene. 100 g of hydroperoxide concentrate contained
 <EMI ID = 37.1>
 
 <EMI ID = 38.1>
 <EMI ID = 39.1>

  
and part of the acetaldehyde formed.

  
Cooled to 20 [deg.] C and the mixture was divided into two equal parts.

  
Analysis of one of these parts showed that 99% of hydroperoxides

  
 <EMI ID = 40.1>

  

 <EMI ID = 41.1>


  
 <EMI ID = 42.1>

  
1.5 g was added. of palladium on activated carbon (catalyst containing 5% palladium) to the other part of the reaction mixture and was introduced into an autoclave. The hydrogenation was carried out at 10 atm., The reaction mixture

  
 <EMI ID = 43.1>

  
of hydrogen absorption.

  
The pressure was then released, the reaction mixture cooled and drawn off. Analysis showed that this mixture was free from ethyl acetate.

  
 <EMI ID = 44.1> <EMI ID = 45.1>

Example 2.

  
 <EMI ID = 46.1>

  
 <EMI ID = 47.1>

  
with sulfuric acid in the presence of acetone.

  
The reaction mixture was neutralized with an aqueous solution of

  
 <EMI ID = 48.1>

  
 <EMI ID = 49.1>

  
 <EMI ID = 50.1>

  

 <EMI ID = 51.1>


  
This mixture was introduced into a 316 stainless steel autoclave.

  
 <EMI ID = 52.1>

  
previously activated. It was treated with hydrogen at 130 [deg.] C and under pressure

  
 <EMI ID = 53.1>

  
catalyst and a mixture B containing:

  

 <EMI ID = 54.1>

Claims (1)

<EMI ID=55.1> <EMI ID=56.1> <EMI ID = 55.1> <EMI ID = 56.1> procédé. process. Exemple 3. Example 3. On a soumis à l'hydrogénation des fractions d'un mélange ayant la composition du mélange A donné dans l'exemple 2. Fractions of a mixture having the composition of mixture A given in Example 2 were hydrogenated. Ces essais d'hydrogénation ont été effectués à une température de 150[deg.]C These hydrogenation tests were carried out at a temperature of 150 [deg.] C <EMI ID=57.1> <EMI ID = 57.1> ci-après : below: <EMI ID=58.1> <EMI ID = 58.1> Après hydrogénation, on a obtenu dans chaque essai, un mélange ayant une composition similaire à celle du mélange B de l'exemple 2. After hydrogenation, in each test, a mixture was obtained having a composition similar to that of mixture B of Example 2. REVENDICATIONS S CLAIMS S 1) Procédé de production, d'éthylphénol à partir de diéthylbenzène, par oxydation du diéthylbenzène en monohydroperoxyde de diéthylbenzène, soutirage du 1) Process for the production of ethylphenol from diethylbenzene, by oxidation of diethylbenzene to diethylbenzene monohydroperoxide, withdrawal of the <EMI ID=59.1> <EMI ID = 59.1> <EMI ID=60.1> <EMI ID = 60.1> solvant consistant en un alcool ou une cétone aliphatique à bas poids moléculaire, puis décomposition de l'hydroperoxyde par contact intime avec un acide fort, de façon à obtenir un mélange de décomposition consistant essentiellement en diéthylbenzène résiduel, éthylphénol, acétaldéhyde, solvant et sous-produits aromatiques oxygénés, caractérisé en ce qu'on traite ce mélange dans des conditinns d'hydrogénation de ces sous-produits aromatiques oxygénés, puis on <EMI ID=61.1> solvent consisting of a low molecular weight alcohol or aliphatic ketone, then decomposition of the hydroperoxide by intimate contact with a strong acid, so as to obtain a decomposition mixture consisting essentially of residual diethylbenzene, ethylphenol, acetaldehyde, solvent and sub- oxygenated aromatic products, characterized in that this mixture is treated in conditions of hydrogenation of these oxygenated aromatic by-products, then <EMI ID = 61.1> atmosphères. atmospheres. <EMI ID=62.1> <EMI ID = 62.1> l'hydrogénation du mélange de décomposition préalablement débarrassé du solvant et de l'acétaldéhyde. hydrogenation of the decomposition mixture previously freed from solvent and acetaldehyde. 5) Procédé suivant revendication 4, caractérisé en ce qu'en effectue l'hydrogé- 5) A method according to claim 4, characterized in that in effect the hydrogen <EMI ID=63.1> <EMI ID = 63.1> 6) Procède suivant revendications 1, 2 et 4, caractérisé en ce qu'on effectue 6) Method according to claims 1, 2 and 4, characterized in that one carries out l'hydrogénation en présence d'un catalyseur à base de métal de transition hydrogenation in the presence of a transition metal catalyst <EMI ID=64.1> <EMI ID = 64.1> <EMI ID=65.1> <EMI ID = 65.1> choisi dans le groupe comprenant le platine, le palladium et leurs alliages, les alliages de cobalt, le nickel et ses alliages, le chromate de cuivre. chosen from the group comprising platinum, palladium and their alloys, cobalt alloys, nickel and its alloys, copper chromate.
BE153388A 1975-02-14 1975-02-14 ETHYLPHENOL PRODUCTION PROCESS BE825563A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BE153388A BE825563A (en) 1975-02-14 1975-02-14 ETHYLPHENOL PRODUCTION PROCESS

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE825563 1975-02-14
BE153388A BE825563A (en) 1975-02-14 1975-02-14 ETHYLPHENOL PRODUCTION PROCESS

Publications (1)

Publication Number Publication Date
BE825563A true BE825563A (en) 1975-05-29

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ID=25648394

Family Applications (1)

Application Number Title Priority Date Filing Date
BE153388A BE825563A (en) 1975-02-14 1975-02-14 ETHYLPHENOL PRODUCTION PROCESS

Country Status (1)

Country Link
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0012613B1 (en) * 1978-12-14 1984-08-08 Mobil Oil Corporation A process for producing 3-alkylphenols and 1,3-dihydroxybenzene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0012613B1 (en) * 1978-12-14 1984-08-08 Mobil Oil Corporation A process for producing 3-alkylphenols and 1,3-dihydroxybenzene

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