DE2025267A1 - Process for the production of Ohgomeri sierungskatalysatoren and use of these catalysts for the oligomerization of oils finen - Google Patents

Description

DR.-ING. FROM KREISLER DR.-! NG. BEAUTIFUL FOREST DR.-ING. TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLÖPSCH

COLOGNE 1, DEICHMANNHAUS

Cologne, 7.5.1970 Kl / Ax / Hz

BP CHEMICALS LIMITED,.

Britannic House, Moor Lane, London, E.C. 2 (England).

Process for the preparation of oligomerization catalysts and using these catalysts to oligomerize olefins

The invention relates to a method for producing Catalysts for the oligomerization of olefins and oligomerization processes, i.e. those using them Catalysts are carried out.

The method according to the invention for the preparation of Oligomerization catalysts are characterized in that one anhydrous potassium compounds with an anhydrous organic solution of a Lithiura hydrocarbon compound impregnated ", the solvent evaporates and the Lithium-hydrocarbon compound decomposes.

Potassium hydroxide and are suitable as potassium compounds Potassium salts of inorganic acids. Suitable potassium salts of anorpjani see acids are the silicates, sulfates and halides. Potassium carbonate is preferred as the potassium salt. The potassium compound can be al3 powder, granules (irregularly shaped bits or pearls) or Pellets are present.

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BATH ORIGINAL,

The hydrocarbon residue of the lithium hydrocarbon compound can be any hydrocarbon radical with. 1 to 30 carbon atoms and from the group consisting of alkyl radicals, cyclo-., alkyl radicals, alkenyl radicals, phenyl radicals,. alkylphenyl radicals. and phenylalkyl radicals. He is preferably an alkyl radical with 2 to 10 carbon atoms »

In general, it is convenient to prepare the catalyst under an inert gas such as argon or helium perform. ·. --- .-

Preferably the hydrocarbon products are the Complete decomposition of the lithium hydrocarbon compound removed as they deactivate the catalyst can. This is usually accomplished by adequate purging with an inert gas during catalyst preparation achieved.

The amount of lithium in the catalyst is preferably between 0.1 and 20 Gewa-yoj, preferably between 0.5 and 5.0% by weight, based on the anhydrous potassium compound.

The catalyst may be subjected to prior to the application of a pretreatment in which it is preferably 30 minutes or longer is heated to a temperature in the range of 50 to 35O ⁰ C with hydrogen at atmospheric pressure or under reduced pressure. It is also possible to rush the catalyst in the presence of hydrogen.

The catalyst oligomerizes olefins such as propylene and n-butenes and cooligomerizes mixtures of olefins such as Propylene-ethylene, n-butene-ethylene, n-penten-ethylene, Isobutene-ethylene, n-butene-propylene or isobutene-propylene.

The olefin oligomers produced with this catalyst are generally less branched than the olefin oligomers, those with other catalysts used for this reaction, including other alkali catalysts like sodium that is based on anhydrous potassium carbonate

• 109815/1996

dispersed can be obtained. With one in the present a catalyst prepared according to the invention carried out cooligomerization reaction of propylene with Ethylene is mainly formed by pentenes and heptenes, with the heptene fraction being more than 50% linear. With other catalysts a heptene fraction is obtained which is mainly composed of branched isomers, e.g. consists of less than 20% linear heptene.

In a further aspect, the invention is directed to Oligomerization of olefins directed by a process which is characterized in that olefins or olefin mixtures are brought together with a catalyst which by impregnating an anhydrous potassium compound with an anhydrous organic solution of a lithium hydrocarbon substance compound, evaporation of the solvent and decomposition of the lithium-hydrocarbon compound has been prepared under temperature and pressure conditions under which the oligomerization takes place.

The oligomerization temperature is expediently in the range from 0 to 250 ⁰ O, preferably in the range from 50 to 250 C. The reaction pressure is expediently under which the reactants are kept in the liquid phase. This pressure is expediently in the range from 0 to 280 atmospheres, preferably in the range between 35 and 140 atmospheres.

When two olefins, e.g. ethylene and propylene, cooligomerize are, the molar ratio of one olefin to the other is expediently in the range from 6: 1 to at the beginning I26, preferably between 4: 1 and 1: 4.

The process can be carried out in the presence or absence of a solvent. Preferred as a solvent become hydrocarbons, e.g. under normal IT conditions liquid paraffins.

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. 2925267

The feedstock is preferably free of impurities such as oxygen, water, sulfur compounds, Dienes or acetylenes, or contains these compounds only in very small proportions. Preferably the total is content of such impurities is less than 0.1% by weight of the olefinic feedstock.

The process can be carried out batchwise or continuously.

The oligomers produced in the process according to the invention are suitable as chemical intermediates for Manufacture of various products such as lubricants, Adhesives, elastomers, plastics, pharmaceutical preparations, insecticides and insect repellants. The heptenes are particularly advantageous for the production of Cg-oxo alcohols by a hydroformylation reaction.

Example 1

50 ml of a 1.5% solution of lithium butyl in dry cyclohexane are added to 25 g of potassium carbonate which has ^{been dried at 200 ° C. and 0.3 rom Hg.} The mixture was stirred at 120 ° C. for 30 minutes, during which the cyclohexane was evaporated. The lithium butyl was decomposed and the catalyst obtained, which contained 2.2% by weight of lithium, was placed in a 1 liter autoclave under dry nitrogen. An ethylene-propylene mixture in a molar ratio of 4: 1 was pressed onto the autoclave up to a pressure of 70 atmospheres. _The: autoclave was then shaken for 17 hours at 15O ⁰ C. The products were blown into flasks immersed in mixtures of solid carbon dioxide and acetone. The products (128 g) were distilled. They contained 33% pentenes, 6% hexenes, 36-6 heptenes, which consisted of 51% linear heptenes, and 25% higher-boiling materials.

Example 2
This example is for comparison purposes only.

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To potassium carbonate which had been dried at 300 ° C. and 0.2 mm Hg, sodium metal was added in such an amount that a dispersion was obtained which contained 4.5% by weight of sodium. The mixture was heated to 200 ° C. with vigorous stirring. A portion of the catalyst obtained (46 g) was placed under an inert gas in a 1 l autoclave, onto which an ethylene-propylene mixture in a molar ratio of 3 ml was forced up to a pressure of 105 °. The autoclave was ^{shaken at 150 °} C. for 17 hours. The products were vented into flasks immersed in mixtures of solid carbon dioxide and acetone. The products (229 g) were distilled. They contained 14% pentenes, 4% hexenes, 57% heptenes, which consisted of 19 $ linear heptenes, and 25% higher boiling material.

A comparison with Example 1 reveals the higher linearity the heptene fraction obtained with the new catalyst recognize.

Example 3

A catalyst was prepared in the manner described in Example 1. A portion of the catalyst obtained (33 »O g), which contained 2.5 wt .-% lithium, was placed under inert gas in a 1 1 autoclave, on which a Geraisch of ethylene and propylene in a molar ratio of 4: 1 to 2u Pressure of 56 atmospheres was applied. The autoclave was ^{shaken at 120 °} C. for 17 hours. The products were vented into flasks immersed in mixtures of solid carbon dioxide and acetone. The products (68 g) were distilled. They contained 30% pentenes, 8% hexenes, 40% heptenes, which were 51% linear, and 22% higher boiling material.

Example 4

A catalyst was prepared in the manner described in Example 1. Part of the catalyst obtained O 9 »7 g), which contained 2.5 wt .-% lithium, was under Put inert gas in a 1 1 autoclave on the one Mixture of ethylene and propylene in a molar ratio of

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3: 1 up to a pressure of 105 atmospheres. The autoclave was ^{shaken at 150 °} C. for 18 hours. The products were vented into flasks immersed in mixtures of solid carbon dioxide and acetone. The products (144 g) were distilled. They contained 52% pentenes, hexenes, 28% heptenes, which were 49% linear, and heavier material.

Example 5

A catalyst was prepared in a manner similar to that in Example 1 described, manufactured. A portion of the obtained catalyst (18.8 g) containing 1.3% by weight of lithium was used placed under inert gas in a 1 1 autoclave on the a mixture of ethylene and propylene in a molar ratio of 3: 1 up to a pressure of 120 atmospheres. The autoclave was shaken at 150 ° C. for 19 hours. The products were blown off in flasks, which in mixtures solid carbon dioxide and acetone dipped. The products (149 s) were distilled. They contained 54% pentenes, 7% hexenes, 23% heptenes which were 51% linear, and 16% heavier material.

Example 6

A catalyst was prepared in a manner similar to that described in Example 1. A portion of the catalyst obtained (49.5 g), which contained 1.5% by weight of lithium, was placed in a 1 l autoclave under inert gas Propylene was injected to a pressure of 84 atmospheres. The autoclave was 1? Shaken at 150 ^° C. for hours. The products were vented into flasks immersed in mixtures of solid carbon dioxide and acetone. The products (64 g) were distilled. They contained 36% hexene and 4% higher boiling material. 86% of the hexenes formed consisted of 4-methyl-pent-1-ene.

Example 7

A catalyst was made in a manner similar to that in Beinpieli described, manufactured. Part of the catalyst obtained

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202526V

Sators (21.5 δ), which contained 1.25 wt .-% lithium, was placed under an inert gas in a 1 l autoclave. ITach introduction of 500 1 of dry pentene-1, 105 ^a tu ethylene pressed. The autoclave was shaken for 17 hours at 15O ⁰ G. The products were vented into flasks immersed in mixtures of solid carbon dioxide and acetone. The products (133 g) were distilled. They contained 89% heptenes, which were 47% linear, and 11% higher boiling material.

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Claims (12)

- 8 claims 1.) Process for the preparation of oligomerization catalysts, characterized in that anhydrous Potassium compounds impregnated with anhydrous organic solutions - organic lithium compounds, the Solvent evaporates and the organolithium Ver. bond decomposed. 2.) Process according to claim 1, characterized in that the anhydrous potassium compounds are potassium hydroxide or potassium salts of inorganic acids, preferably silicates, sulfates, halides or carbonates are used. 3.) Process according to Claims 1 to 2, characterized in that Juan uses organolithium compounds, whose organic radical is an alkyl · ·, cycloalkyl, alkenyl, phenyl, alkylphenyl or phenylalkyl radical with 1 to _ΤΌ Carbon atoms, preferably an alkyl radical having 2 to 10 carbon atoms. 4.) Process according to Claims 1 to 3, characterized in that that the preparation of the catalyst in the presence of an inert gas, preferably argon, nitrogen or helium. 5.) Process according to claims 1 to 4, characterized in that lithium in amounts between C, l and 20, preferably between 0.5 and 5 wt .- ^, based on the anhydrous Potassium compound is applied. 6.) Process according to Claims 1 to 5, characterized in that that the catalyst prior to use with hydrogen at atmospheric pressure or overpressure at temperatures Is pretreated in the range from 50 to 350 ° C. 109815/1996 2Ö252B7 7.) Process according to Claims 1 to 6, characterized in that the catalyst is prepared in the presence of hydrogen. 8.) Use of the catalysts according to Claims 1 to 7 for oligomerization of olefins. 9.) Use according to claim 8 for Oligomerisieruog at temperatures ranging from 0 to 250 ⁰ C ₁ is preferably in the range of 50 to 25O ° C. 10.) Use according to Claims 8 to 9 for oligomerization at pressures in the range from 0 to 280, preferably 35 to 140 atmospheres. 11.) Use according to claims 8 to 10 for the oligomerization of mixtures which contain 2 olefins in an initial molar ratio in the range from 6: 1 to 1: 6, preferably in the range from 4: 1 to 1: 4. 12.) Use according to claims 8 to 11 for oligomerization in the presence or absence of diluents. _Λ 109815/1996