FR2552079A1 - Improved process for the synthesis of 1-butene by ethylene dimerisation. - Google Patents

Improved process for the synthesis of 1-butene by ethylene dimerisation. Download PDF

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FR2552079A1
FR2552079A1 FR8315040A FR8315040A FR2552079A1 FR 2552079 A1 FR2552079 A1 FR 2552079A1 FR 8315040 A FR8315040 A FR 8315040A FR 8315040 A FR8315040 A FR 8315040A FR 2552079 A1 FR2552079 A1 FR 2552079A1
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ethylene
butene
thf
alkyl titanate
aluminum compound
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FR2552079B1 (en
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Le Quan Nhuong
Daniel Cruypelinck
Dominique Commereur
Yves Chauvin
Gerard Leger
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Priority to FR8315040A priority Critical patent/FR2552079B1/en
Priority to EP84401784A priority patent/EP0135441B1/en
Priority to DE8484401784T priority patent/DE3461173D1/en
Priority to NO843713A priority patent/NO158575C/en
Priority to AU33288/84A priority patent/AU572191B2/en
Priority to BR8404694A priority patent/BR8404694A/en
Priority to NZ209604A priority patent/NZ209604A/en
Priority to CA000463662A priority patent/CA1234383A/en
Priority to US06/652,555 priority patent/US4532370A/en
Priority to JP59198390A priority patent/JPS6094923A/en
Publication of FR2552079A1 publication Critical patent/FR2552079A1/en
Priority to US06/728,901 priority patent/US4615998A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron

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

Abstract

Process for the synthesis of 1-butene by dimerisation of ethylene in the presence of a catalyst formed by the interaction, in a hydrocarbon medium, on the one hand, of a trialkylaluminium with, on the other hand, a mixture of an alkyl titanate and of tetrahydrofuran in proportions close to stoichiometry. The activity and the selectivity are better than when tetrahydrofuran is employed as solvent in the dimerisation reaction.

Description

L'objet de la présente invention est un procédé amélioré de dimérisation de l'éthylène en butène-l. The object of the present invention is an improved process for the dimerization of ethylene to butene-1.

Dans le brevet U.S. 2.943.125, K. Ziegler a décrit une méthode de dimérisation de l'éthylène en butène-l au moyen d'un catalyseur obtenu par le mélange de trialkylaluminium et d'un tétraalcoolate de titane ou de zirconium; lors de la réaction se forme également une certaine quantité de poiyéthylène de haute masse moléculaire qui gène considérablement la mise en oeuvre. Plusieurs améliorations ont été proposées pour diminuer le taux de polymère, en particulier dans le brevet U.S. 3.686.350 qui préconise l'emploi de composés organiques du phosphore, conjointement avec les éléments du catalyseur, dans le brevet U.S. 4.101.600 qui revendique le traitement du catalyseur par de l'hydrogène ou dans le brevet U.S. 3.879.485 qui revendique l'utilisation de divers éthers comme solvants du milieu réactionnel.Bien que ces modifications du système catalytique initial apportent une amélioration substantielle à la sélectivité de la réaction, elles se révèlent d'une utilisation peu pratique, en particulier dans un procédé industriel dans lequel il faut pouvoir séparer le butène-l du solvant en laissant seulement des traces de composé polaire dans le butène. In U.S. Patent 2,943,125, K. Ziegler described a method of dimerization of ethylene to butene-1 using a catalyst obtained by the mixture of trialkylaluminum and a titanium or zirconium tetraalcoholate; during the reaction also forms a certain amount of high molecular weight polyethylene which considerably hinders the processing. Several improvements have been proposed to reduce the level of polymer, in particular in US Pat. No. 3,686,350 which recommends the use of organic phosphorus compounds, together with the elements of the catalyst, in US Pat. No. 4,101,600 which claims the treatment of the catalyst by hydrogen or in US Pat. No. 3,879,485 which claims the use of various ethers as solvents of the reaction medium. Although these modifications of the initial catalytic system bring a substantial improvement to the selectivity of the reaction, they are reveal an impractical use, in particular in an industrial process in which it is necessary to be able to separate the butene-1 from the solvent, leaving only traces of polar compound in the butene.

II a maintenant été trouvé, et ceci constitue l'objet de la présente invention, que le tétrahydrofuranne (THF) associé à un titanate d'alkyle en quantité voisine de la stoechiométrie et à un tryhydrocarbylaluminium améliore appréciablement l'activité et la sélectivité des catalyseur titanate d'alkyle-trihydrocarbylaluminium dans dimérisation de l'éthylène en butène-l. Cet effet est plus marqué que celui qui est apporté par les coordinats revendiqués jusqu'à présent, tels que les phosphites ou les amines, et il est également plus marqué que celui apporté par l'utilisation d'éthers en quantité correspondant à un usage comme solvant. Il présente également l'avantage d'éliminer l'emploi des dits éthers comme solvants, dont on a signalé les inconvénients (difficultés de séparation).L'emploi de THF associé au tétraalkyltitanate en quantités voisines de la stoechiométrie permet même d'éviter l'usage de tout solvant, et les constituants du catalyseur peuvent être mélangés directement au sein d'un des produits ou des sous produits de la réaction, ce qui évite la consommation ou le recyclage du dit solvant, toujours difficile à séparer d'un mélange issu d'une oligomérisation. It has now been found, and this constitutes the object of the present invention, that tetrahydrofuran (THF) associated with an alkyl titanate in an amount close to stoichiometry and with a tryhydrocarbylaluminum appreciably improves the activity and the selectivity of the catalysts. alkyl titanate-trihydrocarbylaluminium in dimerization of ethylene in butene-1. This effect is more marked than that provided by the ligands claimed so far, such as phosphites or amines, and it is also more marked than that provided by the use of ethers in an amount corresponding to a use as solvent. It also has the advantage of eliminating the use of said ethers as solvents, the drawbacks of which have been pointed out (separation difficulties). The use of THF associated with tetraalkyltitanate in amounts close to stoichiometry even makes it possible to avoid the use of any solvent, and the constituents of the catalyst can be mixed directly within one of the products or by-products of the reaction, which avoids the consumption or recycling of said solvent, which is always difficult to separate from a mixture from an oligomerization.

Par quantité voisine de la stoechiométrie on entend que le THF
est utilisé en mélange avec le tétraalkyltitanate dans un rapport molaire de 0,5 à 10, de préférence 1 à 3, plus particulièrement 2 moles de THF par mole de composé du titane. Sans être lié à aucune théorie, on peut penser que le THF se complexe sur l'atome de titane permettant l'hexacoordination que le titane ne réalise autrement qu'en s'auto associant. Si on met en oeuvre le THF dans des rapports supérieurs à 10, tels que 20 et au-delà, ou si il est utilisé comme solvant de réaction on observe que la réaction est considérablement ralentie et que sa sélectivité est moins bonne.By quantity close to stoichiometry means that THF
is used in admixture with tetraalkyltitanate in a molar ratio of 0.5 to 10, preferably 1 to 3, more particularly 2 moles of THF per mole of titanium compound. Without being bound to any theory, we can think that THF is complex on the titanium atom allowing the hexacoordination that titanium does not achieve other than by associating itself. If THF is used in ratios greater than 10, such as 20 and beyond, or if it is used as reaction solvent, it is observed that the reaction is considerably slowed down and that its selectivity is less good.

Les composés de l'aluminium utilisés pour préparer le catalyseur sont représentés par les formules générales A1R3 ou A1R2H dans lesquelles R est un radical hydrocarbyl, de préférence alkyle comprenant de 2 à 6 atomes de carbone, par exemple le triéthylaluminium, le tripropylaluminium, le triisobutylaluminium, l'hydrure de diisobutylaluminium, le trihexylaluminium. The aluminum compounds used to prepare the catalyst are represented by the general formulas A1R3 or A1R2H in which R is a hydrocarbyl radical, preferably alkyl comprising from 2 to 6 carbon atoms, for example triethylaluminium, tripropylaluminium, triisobutylaluminium , diisobutylaluminium hydride, trihexylaluminium.

Les titanates d'alkyle utilisés dans l'invention répondent à la formule générale Ti (OR')4 dans laquelle R' est un radical alkyle linéaire ou ramifié comportant de 2 à 8 atomes de carbone. On peut utiliser par exemple le titanate de tétraéthyle, le titanate de tétraisopropyle, le titanate de tétra-n-butyle, le titanate de tétra-2-éthyl-hexyle.  The alkyl titanates used in the invention correspond to the general formula Ti (OR ') 4 in which R' is a linear or branched alkyl radical containing from 2 to 8 carbon atoms. One can use for example tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethyl-hexyl titanate.

Le composé de l'aluminium, le composé du titane et le THF sont
mis en contact au sein d'un hydrocarbure et/ou d'un ou des produits
d'oligomérisation tels que les hexènes, de préférence en présence
d'éthylène. Le rapport molaire entre le composé de l'aluminium
et celui du titane est d'environ 1:1 à 20:1 et de préférence de environ
2:1 à 5:1. La concentration du titane dans la solution ainsi préparée
est avantageusement comprise entre 10 4 et 0,5 mole par litre et
de préférence entre 2.10 3 et 0,1 mole par litre. La température
à laquelle se fait le mélange est habituellement comprise entre -10 et450C et de préférence entre O et 300C.La quantité d'éthylène
présent dans le milieu correspond de préférence à la saturation de
la solution à la température considérée et à la pression d'une atmos
phère ou davantage.The aluminum compound, the titanium compound and THF are
brought into contact within a hydrocarbon and / or one or more products
oligomerization such as hexenes, preferably in the presence
ethylene. The molar ratio between the aluminum compound
and that of titanium is from about 1: 1 to 20: 1 and preferably from about
2: 1 to 5: 1. The concentration of titanium in the solution thus prepared
is advantageously between 10 4 and 0.5 mole per liter and
preferably between 2.10 3 and 0.1 mole per liter. Temperature
at which the mixing takes place is usually between -10 and 450C and preferably between 0 and 300C. The amount of ethylene
present in the medium preferably corresponds to the saturation of
the solution at the temperature considered and at the pressure of one atmos
sphere or more.

La solution de catalyseur ainsi obtenue peut être utilisée telle
quelle ou elle peut être diluée par addition des produits de la réaction.The catalyst solution thus obtained can be used as
which can be diluted by adding the reaction products.

Dans un mode particulier de mise en oeuvre de la réaction cataly
tique de dimérisation en discontinu, on introduit un volume choisi
de la solution catalytique, préparée comme décrit ci-dessus, dans
un réacteur muni des habituels systèmes d'agitation et de refroidis
sement, puis on pressurise par de l'éthylène à une pression de préfé
rence comprise entre 0,5 et 8 MPa et on maintient la température
entre 20 et 700C, de préférence entre 50 et 70"C. On alimente
le réacteur par de l'éthylène à pression constante jusqu'à ce que
le volume total de liquide produit représente entre 2 et 50 fois le
volume de la solution catalytique primitivement introduit ; on détruit
alors le catalyseur et on soutire et sépare les produits de la réaction
et le solvant éventuel.In a particular embodiment of the cataly reaction
batch dimerization tick, a selected volume is introduced
of the catalytic solution, prepared as described above, in
a reactor fitted with the usual stirring and cooling systems
then pressurized with ethylene at a preferred pressure
between 0.5 and 8 MPa and the temperature is maintained
between 20 and 700C, preferably between 50 and 70 "C. We supply
the reactor with ethylene at constant pressure until
the total volume of liquid produced represents between 2 and 50 times the
volume of the catalytic solution originally introduced; we destroy
then the catalyst and the reaction products are drawn off and separated
and any solvent.

En cas d'opération continue, la mise en oeuvre est de préférence
la suivante: la solution catalytique est injectée en même temps
que l'éthylène dans un réacteur agité par les moyens classiques ou
par recirculation extérieure. La température est maintenue entre
environ 200C et 70"C et la pression est suffisante pour que tous les composés se trouvent en phase liquide; selon les débits de catalyseur et de l'éthylène cette pression sera comprise entre 0,5 et 8 MPa.In case of continuous operation, the implementation is preferably
the following: the catalytic solution is injected at the same time
that ethylene in a reactor stirred by conventional means or
by external recirculation. The temperature is maintained between
about 200C and 70 "C and the pressure is sufficient for all the compounds to be in the liquid phase; depending on the flow rates of catalyst and ethylene this pressure will be between 0.5 and 8 MPa.

Par une vanne de détente qui maintient la pression constante, s'écoule une partie du mélange réactionnel à un débit massique égal au débit massique des fluides introduits. Le fluide ainsi détendu est envoyé dans un système de colonnes à distiller qui permet de séparer le butène-l de ltéthylène d'une part, qui est renvoyé au réacteur, des hexènes et des octènes d'autre part, dont une partie est renvoyée dans la section de préparation du catalyseur. Le pied de colonne contenant le catalyseur et les produits lourds est incinéré.By means of an expansion valve which keeps the pressure constant, part of the reaction mixture flows at a mass flow rate equal to the mass flow rate of the fluids introduced. The fluid thus expanded is sent to a system of distillation columns which makes it possible to separate butene-1 from ethylene on the one hand, which is returned to the reactor, from hexenes and octenes on the other hand, part of which is returned to the catalyst preparation section. The column bottom containing the catalyst and the heavy products is incinerated.

Les exemples suivants illustrent l'invention sans en limiter la portée. The following examples illustrate the invention without limiting its scope.

Exemple I
Dans un autoclave de type Grignard en acier inoxydable d'un volume de 250ml, muni d'une double enveloppe permettant de réguler la température à 180C par circulation d'eau, on introduit dans l'ordre, sous atmosphère d'éthylène: 2,5ml d'une solution de triéthylaluminium dans une coupe d'hexène préparée en mélangeant 0,25ml de triéthylaluminium avec 9,75ml d'hexènes, puis une solution d'un complexe titanate de tétra-n-butyle-tétrahydrofuranne préparée en mélangeant 0,05ml de titanate de tétra-n-butyle avec 0,024ml de tétrahydrofuranne et 2,42ml de coupe hexènes. Le rapport molaire entre le tétrahydrofuranne et le titanate est égal à 2,1:1. Après 2 minutes d'interaction, la température est portée à 55 C et la pression d'éthylène à 2 MPa.Example I
In an autoclave of the Grignard type in stainless steel with a volume of 250 ml, provided with a double envelope making it possible to regulate the temperature to 180C by circulation of water, the following are introduced in order, under an ethylene atmosphere: 2, 5 ml of a solution of triethylaluminium in a hexene cup prepared by mixing 0.25 ml of triethylaluminium with 9.75 ml of hexenes, then a solution of a tetra-n-butyl titanate-tetrahydrofuran complex prepared by mixing 0, 05ml of tetra-n-butyl titanate with 0.024ml of tetrahydrofuran and 2.42ml of hexene cut. The molar ratio between tetrahydrofuran and titanate is 2.1: 1. After 2 minutes of interaction, the temperature is brought to 55 ° C. and the ethylene pressure to 2 MPa.

Après 2h30 de réaction, I'introduction d'éthylène est arrêtée et le catalyseur est détruit par injection sous pression de 2ml d'eau. On a consommé au total 133g d'éthylène. After 2.5 hours of reaction, the introduction of ethylene is stopped and the catalyst is destroyed by injection under pressure of 2 ml of water. A total of 133g of ethylene was consumed.

Outre l'éthylène qui n'a pas réagi, on recueille: 0,28g de n-butane, 92,40g de butène-l, 6,46g d'hexènes, 0,17g d'octènes et 0,0027g de polyéthylène. L'analyse de la fraction C4 par chromatographie en phase gazeuse avec un détecteur à ionisation de flamme montre une teneur en butène-2 total inférieure à 10ppm. Le polyéthylène représente 27ppm. In addition to the unreacted ethylene, there are collected: 0.28 g of n-butane, 92.40 g of butene-1, 6.46 g of hexenes, 0.17 g of octenes and 0.0027 g of polyethylene. Analysis of fraction C4 by gas chromatography with a flame ionization detector shows a total butene-2 content of less than 10 ppm. Polyethylene represents 27ppm.

Dans ces conditions, la productivité du catalyseur s'élève à 13088g de butène-l par g de titanate métal. Under these conditions, the productivity of the catalyst amounts to 13088 g of butene-1 per g of titanate metal.

Exemple 2 (comparaison- ne fait pas partie de l'invention)
Dans le même appareillage que celui qui a été utilisé dans l'exem- ple 1 et toutes choses égales par ailleurs, on a augmenté la quantité de tétrahydrofuranne introduite de façon à avoir un rapport molaire tétrahydrofuranne sur titanate de 20:1 au lieu de 2,1:1. On n'a constaté aucune conversion de l'éthylène après 5h à 55"C. Example 2 (comparison - not part of the invention)
In the same apparatus as that which was used in example 1 and all other things being equal, the quantity of tetrahydrofuran introduced was increased so as to have a tetrahydrofuran to titanate molar ratio of 20: 1 instead of 2 , 1: 1. No conversion of ethylene was observed after 5 h at 55 ° C.

Exemple 3 (ne fait pas partie de l'invention)
Dans le même appareillage que celui qui a été utilisé dans l'exemple
1 et dans les mêmes conditions à ceci près qu'on a introduit 2 fois plus du composé du titane, deux fois plus du composé de l'aluminium et pas de tétrahydrofuranne, on a obtenu 91,6g de butène-l, 0,28g de butane, 11,8g d'hexènes, 0,68g d'octènes et 0,1g de polyéthylène.Example 3 (not part of the invention)
In the same apparatus as that which was used in the example
1 and under the same conditions except that 2 times more of the titanium compound was introduced, twice as much of the aluminum compound and no tetrahydrofuran, 91.6 g of butene-1 was obtained, 0.28 g butane, 11.8g of hexenes, 0.68g of octenes and 0.1g of polyethylene.

Le butène-l contient 360ppm de butène-2. La productivité du catalyseur n'est que de 6.500g de butène par g de Ti métal.  Butene-1 contains 360 ppm of butene-2. The productivity of the catalyst is only 6,500 g of butene per g of Ti metal.

Claims (8)

REVENDICATIONS 1. Procédé amélioré de conversion de l'éthylène en butène-l, dans1. Improved process for converting ethylene to butene-1, in lequel on met l'éthylène en contact avec une solution d'un cataly which ethylene is brought into contact with a solution of a cataly seur résultant de l'interaction d'un titanate d'alkyle, de tétra sor resulting from the interaction of an alkyl titanate, tetra hydrofuranne THF) et d'un composé d'aluminium de formule ALR3 hydrofuran THF) and an aluminum compound of formula ALR3 ouALR211 dans laquelle chacun des restes R est un radical hydro ouALR211 in which each of the R residues is a hydro radical aryle, caractérisé en ce que le THF et le titanate d'alkyle aryl, characterized in that THF and alkyl titanate sont mis en oeuvre dans un rapport molaire de 1:1 à 5:1.  are used in a molar ratio of 1: 1 to 5: 1. 2. Procédé selon la revendication 1 dans lequel le rapport molaire2. Method according to claim 1 wherein the molar ratio du THF au titanate d'alkyle est d'environ 2:1 THF to alkyl titanate is about 2: 1 3. Procédé selon la revendication 1 ou 2, dans lequel le catalyseur3. Method according to claim 1 or 2, wherein the catalyst résulte de l'interaction du composé d'aluminium avec une solution results from the interaction of the aluminum compound with a solution préformée du titanate d'alkyle et de THF dans un hydrocarbure. preformed alkyl titanate and THF in a hydrocarbon. 4. Procédé selon l'une des revendications 1 à 3, dans lequel le cataly4. Method according to one of claims 1 to 3, wherein the cataly seur est formé dans un hydrocarbure sature. its formed in a saturated hydrocarbon. 5. Procédé selon l'une des revendications 1 à 3 dans lequel le cataly5. Method according to one of claims 1 to 3 wherein the cataly seur est formé dans les hexènes recueillis comme sous produits sor is formed in the hexenes collected as byproducts dans la réaction de conversion de l'éthylène en butène-l. in the reaction for converting ethylene to butene-1. 6. Procédé selon l'une des revendications 1 à 5, dans lequel6. Method according to one of claims 1 to 5, wherein l'interaction du titanate d'alkyle, du THF et du composé d'alu the interaction of alkyl titanate, THF and aluminum compound minium est effectuée à une température de -10 à 450C et la mise minium is carried out at a temperature of -10 to 450C and the setting en contact de l'éthylène avec le catalyseur, dans le but de con in contact of ethylene with the catalyst, in order to con vertir l'éthylène en butène-l, est effectuée à 50-700C.  to turn ethylene into butene-1, is carried out at 50-700C. 7. Procédé selon l'une des revendications I à 6 dans lequel le rapport7. Method according to one of claims I to 6 wherein the report molaire entre le composé de l'aluminium et le composé de titane molar between the aluminum compound and the titanium compound est de 1:1 à 20:1, et la concentration du titane est comprise entre 10 4 et 0,5 mole par litre.  is 1: 1 to 20: 1, and the concentration of titanium is between 10 4 and 0.5 mole per liter. 8. Procédé selon l'une des revendications I à 5 dans lequel la tempé 8. Method according to one of claims I to 5 wherein the temperature rature de la réaction de dimérisation est de 20 à 70"C et la the size of the dimerization reaction is 20 to 70 "C and the pression de 0,5 à 8MPa.  pressure from 0.5 to 8MPa.
FR8315040A 1983-09-20 1983-09-20 IMPROVED PROCESS FOR THE SYNTHESIS OF BUTENE-1 BY DIMERIZATION OF ETHYLENE Expired FR2552079B1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
FR8315040A FR2552079B1 (en) 1983-09-20 1983-09-20 IMPROVED PROCESS FOR THE SYNTHESIS OF BUTENE-1 BY DIMERIZATION OF ETHYLENE
EP84401784A EP0135441B1 (en) 1983-09-20 1984-09-11 Process for the synthesis of butene-1 by dimerisation of ethylene
DE8484401784T DE3461173D1 (en) 1983-09-20 1984-09-11 Process for the synthesis of butene-1 by dimerisation of ethylene
NO843713A NO158575C (en) 1983-09-20 1984-09-18 PROCEDURE FOR THE CONVERSION OF THE ETHYLE TO BUTEN-I.
BR8404694A BR8404694A (en) 1983-09-20 1984-09-19 IMPROVED PROCESS FOR CONVERSION OF ETHYLENE TO BUTENE-1
NZ209604A NZ209604A (en) 1983-09-20 1984-09-19 Catalytic production of 1-butene from ethylene
AU33288/84A AU572191B2 (en) 1983-09-20 1984-09-19 Synthesizing i-butene by dimerisation of ethylene
CA000463662A CA1234383A (en) 1983-09-20 1984-09-20 Improved catalyst and process for the synthesis of butene-1 by ethylene dimerization
US06/652,555 US4532370A (en) 1983-09-20 1984-09-20 Process for synthesizing 1-butene by dimerization of ethylene
JP59198390A JPS6094923A (en) 1983-09-20 1984-09-20 Improved synthesis of 1-butene by dimerization of ethylene
US06/728,901 US4615998A (en) 1983-09-20 1985-04-30 Catalyst suitable for synthesizing 1-butene by dimerization of ethylene

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